CN113105466A - Benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base and preparation method thereof - Google Patents
Benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base and preparation method thereof Download PDFInfo
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 59
- -1 Benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base Chemical class 0.000 title claims abstract description 38
- 239000002262 Schiff base Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 88
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- LZIGUAARBUESJK-UHFFFAOYSA-N benzaldehyde 1H-benzimidazole Chemical compound N1=CNC2=C1C=CC=C2.C(C2=CC=CC=C2)=O LZIGUAARBUESJK-UHFFFAOYSA-N 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- UOQXIWFBQSVDPP-UHFFFAOYSA-N 4-fluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1 UOQXIWFBQSVDPP-UHFFFAOYSA-N 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052742 iron Inorganic materials 0.000 abstract description 6
- 239000007850 fluorescent dye Substances 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 14
- 238000010992 reflux Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000004753 Schiff bases Chemical class 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001556 benzimidazoles Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
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- C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
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Abstract
The application belongs to the field of fluorescent probes, and particularly relates to a benzimidazolyl benzaldehyde rhodamine hydrazine hydrate Schiff base fluorescent probe which utilizes a photoinduced electron transfer mechanism to open a fluorescent switch in the presence of iron ions to form a new compound, wherein the ultraviolet absorption generates red shift, and the fluorescence generates red shift and is obviously enhanced.
Description
Technical Field
The invention relates to benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base and a preparation method thereof.
Background
Benzimidazole is a heterocyclic compound containing two nitrogen atoms, is a very important organic synthetic intermediate, and is widely applied to synthesis of medicine and pesticide intermediates and preparation of dyes and photoconductors. The nitrogen atom on the ring has a lone pair of electrons, so that it can coordinate and adsorb various metals, and can form various ligand structures such as monodentate, multidentate, and cyclic structures, and thus the role of benzimidazole in coordination chemistry is becoming increasingly important.
The rhodamine 6G is in a red or yellow-brown powder shape. Dissolving in water to show scarlet green fluorescence; dissolved in alcohol and shows red and yellow fluorescence or yellow and red and green fluorescence. The metal can be measured photometrically by using the generated ion association complex; can be used as an adsorption indicator and a biological stain, and has wide application.
The Schiff base is usually formed by condensing amine and active carbonyl, has a special conjugated structure and good chemical coordination performance, and part of metal complexes of the Schiff base have good fluorescence performance, so that the Schiff base can be used as a fluorescent probe to identify metal ions, thereby leading to deeper theoretical and application research of people. Meanwhile, Schiff base compounds and metal complexes thereof are also important in the fields of medicine, catalysis, analytical chemistry, corrosion and photochromism. The characteristics of benzimidazole compounds and Schiff bases are organically combined to prepare the benzimidazole Schiff bases, the synthesized compounds have good specific selectivity on iron ions, and the detection limit reaches the nanometer level.
The invention content is as follows:
the invention aims to provide a novel benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base which has a special conjugated structure and good chemical coordination performance, and the synthesis process has the advantages of simplicity in operation, high yield, low cost, quickness in detection and the like.
The invention also aims to provide a preparation method of the benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base.
The invention also aims to provide the application of the benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the compound is mainly applied to the field of materials or sensors;
a preparation method of benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base comprises the following steps:
1) weighing benzimidazole and anhydrous potassium carbonate, and dissolving in a solvent;
2) adding p-fluorobenzaldehyde into the mixed solution under stirring at the constant temperature of 60-120 ℃, continuously reacting for 10-25 h, cooling to room temperature, extracting with ethyl acetate, taking supernatant, distilling under reduced pressure, performing column chromatography separation, and performing vacuum drying to obtain benzimidazole benzaldehyde;
3) weighing rhodamine 6G, and measuring hydrazine hydrate to dissolve in a solvent;
4) reacting the solution prepared in the step 3) for 6-15h under constant temperature stirring at 60-80 ℃, cooling to room temperature, performing suction filtration, recrystallizing, purifying, and drying in vacuum to obtain rhodamine hydrazine hydrate;
5) weighing the benzimidazole benzaldehyde obtained in the step 2) and the rhodamine hydrazine hydrate obtained in the step 4), dissolving in a solvent, adding glacial acetic acid, reacting at a constant temperature of 60-80 ℃ for 3-12 h, cooling to room temperature, crystallizing, filtering, and drying in vacuum to obtain a white powdery solid, namely a final product.
And (3) putting the solution into a three-neck flask provided with a thermometer and a stirring device, adding glacial acetic acid, stirring at a constant temperature of 60-80 ℃ for reaction for 3-12 h, carrying out reduced pressure distillation to remove the solvent to obtain a white powdery solid, recrystallizing and purifying by using methanol, ethanol, chloroform or ethyl acetate, and carrying out vacuum drying to obtain the benzimidazole benzaldehyde rhodamine 6G hydrazine hydrate Schiff base.
Preferably, the solvent is one of N, N-dimethylformamide, dimethyl sulfoxide and ethanol;
preferably, the molar ratio of the benzimidazole to the p-fluorobenzaldehyde in the step 2) is 1: 1-1: 2; more preferably, the molar ratio of benzimidazole to p-fluorobenzaldehyde is 1: 1.2;
preferably, the molar ratio of rhodamine 6G to hydrazine hydrate in the step 4) is 1: 1-1: 5;
the synthesis route of the benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base is as follows:
the benzimidazole and p-fluorobenzaldehyde are reacted to prepare benzimidazole benzaldehyde, rhodamine 6G is reacted with hydrazine hydrate to prepare rhodamine hydrazine hydrate, the benzimidazole benzaldehyde and p-fluorobenzaldehyde react to prepare rhodamine hydrazine hydrate Schiff base, and the compound has good selectivity on metal iron ions through tests (the result is shown in figure 2).
The novel compound can be used as a probe to be applied to the field of ion detection. Although researchers have carried out a lot of reactions by utilizing benzimidazole, compared with similar compounds, the compound has good specific selectivity on iron ions, the detection limit reaches the nanometer level, and meanwhile, the compound has the characteristic of quick response.
The selection mechanism of the compound on metal ions is a photoinduced electron transfer mechanism, rhodamine 6G has strong fluorescence, the fluorescence intensity of an internal hydrazide formed by the reaction of rhodamine 6G and hydrazine hydrate is extremely weak, then benzimidazole benzaldehyde is used for modifying, the obtained compound is finally formed, before the compound is not combined with the metal ions, sensor molecules are shown to be fluorescence quenching, and once a bonding group is combined with a specific metal ion, the fluorescence group emits fluorescence, so that strong fluorescence is shown.
(1) FIG. 1 shows the NMR spectra of the compound of example 1 (the other compounds are also shown).
(2) FIG. 2 is a fluorescence spectrum of the selectivity of the compound benzimidazole benzaldehyde rhodamine lactohydrazide Schiff base on different metal ions (the abscissa is the emission wavelength, and the ordinate is the fluorescence intensity).
In order to better understand the technical solution of the present invention, the following detailed description is made with specific examples.
Example 1
1.18g (10mmol) of benzimidazole, 2.07g (15mmol) of potassium carbonate and 1.24g (10mmol) of p-fluorobenzaldehyde were dissolved in 20mL of N, N-dimethylformamide and introduced into a 100mL three-necked flask equipped with a thermometer and a stirrer. Reacting for 16h under stirring at constant temperature of 100 ℃, cooling to room temperature, extracting, filtering, separating by column chromatography, washing with warm water, recrystallizing with absolute ethyl alcohol, and vacuum drying at 50 ℃ for 8h to obtain the benzimidazole benzaldehyde.
Weighing rhodamine 6G4.79g (10mmol), dissolving in 40ml of hot ethanol, dropwise adding 0.63ml (10mmol) of hydrazine hydrate 80%, refluxing and stirring the mixed solution for reaction for 8 hours until the fluorescence of the solution disappears, cooling to room temperature, separating out light pink solid, washing with hot ethanol for three times, and recrystallizing with acetonitrile to obtain the rhodamine hydrazine hydrate.
2.22g (10mmol) of benzimidazole benzaldehyde and 4.28g (10mmol) of rhodamine hydrazine hydrate are weighed, dissolved in 20mL of hot ethanol, and added to a 100mL three-necked flask equipped with a thermometer and a stirring device. And (3) adding 0.40g (7mmol) of glacial acetic acid into the mixed solution, carrying out reflux reaction for 5h at the constant temperature of 80 ℃ under stirring, cooling to room temperature, separating out a white solid, washing with cold ethanol, and carrying out vacuum drying at 50 ℃ for 8h to obtain the final product, namely the benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base). Yield: 79 percent.
Example 2
01.18g (10mmol) of benzimidazole, 2.07g (15mmol) of potassium carbonate and 1.49g (12mmol) of p-fluorobenzaldehyde were weighed, dissolved in 20mL of N, N-dimethylformamide and added to a 100mL three-necked flask equipped with a thermometer and a stirrer. Reacting for 18h at the constant temperature of 110 ℃ under stirring, extracting, filtering, separating by column chromatography, washing with warm water, recrystallizing with absolute ethyl alcohol, and vacuum drying at 50 ℃ for 8h to obtain the benzimidazole benzaldehyde.
Weighing rhodamine 6G4.79g (10mmol), dissolving in 40ml of hot ethanol, dropwise adding 1.28ml (20mmol) of hydrazine hydrate 80%, refluxing and stirring the mixed solution for reaction for 8 hours until the fluorescence of the solution disappears, cooling to room temperature, separating out light pink solid, washing with hot ethanol for three times, and recrystallizing with acetonitrile to obtain the rhodamine hydrazine hydrate.
2.22g (10mmol) of benzimidazole benzaldehyde and 5.13g (12mmol) of rhodamine hydrazine hydrate are weighed, dissolved in 20mL of hot ethanol, and added to a 50mL three-necked flask equipped with a thermometer and a stirring device. Adding 1.15g (20mmol) of glacial acetic acid into the mixed solution, carrying out reflux reaction for 6h at the constant temperature of 80 ℃ under stirring, cooling to room temperature, separating out a white solid, washing with cold ethanol, and carrying out vacuum drying at 50 ℃ for 8h to obtain the final product compound (benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base). Yield: 82 percent.
Example 3
1.18g (10mmol) of benzimidazole, 2.07g (10mmol) of potassium carbonate and 1.73 g (14mmol) of p-fluorobenzaldehyde were dissolved in 100mL of N, N-dimethylformamide and introduced into a 250mL three-necked flask equipped with a thermometer and a stirrer. Reacting at 100 deg.C under stirring for 20 hr, cooling to room temperature, extracting, vacuum filtering, separating by column chromatography, washing with warm water, recrystallizing with anhydrous ethanol, and vacuum drying at 50 deg.C for 8 hr to obtain benzimidazole benzaldehyde.
Weighing rhodamine 6G4.79g (10mmol), dissolving in 50ml of hot ethanol, dropwise adding 1.61ml (25mmol) of hydrazine hydrate 80%, refluxing and stirring the mixed solution for reaction for 6 hours until the fluorescence of the solution disappears, cooling to room temperature, separating out a light pink solid, washing with hot ethanol for three times, and recrystallizing with acetonitrile to obtain the rhodamine hydrazine hydrate.
2.22g (10mmol) of benzimidazole benzaldehyde and 5.99g (14mmol) of rhodamine hydrazine hydrate are weighed, dissolved in 70mL of hot ethanol, and added to a 100mL three-necked flask equipped with a thermometer and a stirring device. Adding 1.15g (20mmol) of glacial acetic acid into the mixed solution, carrying out reflux reaction for 8h at the constant temperature of 80 ℃ under stirring, cooling to room temperature, separating out a white solid, washing with cold ethanol, and carrying out vacuum drying at 50 ℃ for 8h to obtain a final product compound (benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base). Yield: 77 percent.
Example 4
1.18g (10mmol) of benzimidazole, 2.07g (15mmol) of potassium carbonate and 1.98 g (16mmol) of p-fluorobenzaldehyde were dissolved in 50mL of N, N-dimethylformamide and introduced into a 100mL three-necked flask equipped with a thermometer and a stirrer. Reacting for 10h under stirring at constant temperature of 100 ℃, cooling to room temperature, extracting, filtering, separating by column chromatography, washing with warm water, recrystallizing with absolute ethyl alcohol, and vacuum drying at 50 ℃ for 8h to obtain the benzimidazole benzaldehyde.
Weighing rhodamine 6G4.79g (10mmol), dissolving in 60ml of hot ethanol, dropwise adding 1.92ml (30mmol) of hydrazine hydrate 80%, refluxing and stirring the mixed solution for reaction for 8 hours until the fluorescence of the solution disappears, cooling to room temperature, separating out light pink solid, washing with hot ethanol for three times, and recrystallizing with acetonitrile to obtain the rhodamine hydrazine hydrate.
2.22g (10mmol) of benzimidazole benzaldehyde and 6.85g (16mmol) of rhodamine hydrazine hydrate are weighed, dissolved in 700mL of hot ethanol, and added to a 100mL three-necked flask equipped with a thermometer and a stirring device. Adding 1.15g (20mmol) of glacial acetic acid into the mixed solution, carrying out reflux reaction for 5h at the constant temperature of 80 ℃ under stirring, cooling to room temperature, separating out a white solid, washing with cold ethanol, and carrying out vacuum drying at 50 ℃ for 8h to obtain a final product compound (benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base). Yield: 74 percent.
Example 5
1.18g (10mmol) of benzimidazole, 3.21g (15mmol) of potassium carbonate and 2.23 g (18mmol) of p-fluorobenzaldehyde were dissolved in 40mL of N, N-dimethylformamide and the resulting solution was put in a 100mL three-necked flask equipped with a thermometer and a stirrer. Reacting for 18h at constant temperature of 100 ℃ under stirring, cooling to room temperature, extracting, filtering, separating by column chromatography, washing with warm water, recrystallizing with absolute ethyl alcohol, and vacuum drying at 50 ℃ for 8h to obtain the benzimidazole benzaldehyde.
Weighing rhodamine 6G4.79g (10mmol), dissolving in 40ml of hot ethanol, dropwise adding 2.58ml (40mmol) of hydrazine hydrate 80%, refluxing and stirring the mixed solution for reaction for 6 hours until the fluorescence of the solution disappears, cooling to room temperature, separating out a pink solid, washing with hot ethanol for three times, and recrystallizing with acetonitrile to obtain the rhodamine hydrazine hydrate.
2.22g (10mmol) of benzimidazole benzaldehyde and 7.71g (18mmol) of rhodamine hydrazine hydrate are weighed, dissolved in 30mL of hot ethanol, and added to a 50mL three-necked flask equipped with a thermometer and a stirring device. And (3) adding 0.22g (4mmol) of glacial acetic acid into the mixed solution, carrying out reflux reaction for 5h at the constant temperature of 80 ℃ under stirring, cooling to room temperature, separating out a white solid, washing with cold ethanol, and carrying out vacuum drying at 50 ℃ for 8h to obtain a final product compound (benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base). Yield: 71 percent.
Example 6
1.18g (10mmol) of benzimidazole, 2.07g (15mmol) of potassium carbonate and 2.48g (20mmol) of p-fluorobenzaldehyde were dissolved in 20mL of N, N-dimethylformamide and introduced into a 100mL three-necked flask equipped with a thermometer and a stirrer. Reacting for 10h under stirring at constant temperature of 100 ℃, cooling to room temperature, extracting, filtering, separating by column chromatography, washing with warm water, recrystallizing with absolute ethyl alcohol, and vacuum drying at 50 ℃ for 8h to obtain the benzimidazole benzaldehyde.
Weighing rhodamine 6G4.79g (10mmol), dissolving in 40ml of hot ethanol, dropwise adding 3.23ml (50mmol) of hydrazine hydrate 80%, refluxing and stirring the mixed solution for reaction for 8 hours until the fluorescence of the solution disappears, cooling to room temperature, separating out a pink solid, washing with hot ethanol for three times, and recrystallizing with acetonitrile to obtain the rhodamine hydrazine hydrate.
0.22g (1mmol) of benzimidazole benzaldehyde and 0.86g (2mmol) of rhodamine hydrazine hydrate are weighed, dissolved in 20mL of hot ethanol, and added to a 50mL three-necked flask equipped with a thermometer and a stirring device. And (3) adding 0.31g (5mmol) of glacial acetic acid into the mixed solution, carrying out reflux reaction for 6h at the constant temperature of 80 ℃ under stirring, cooling to room temperature, separating out a white solid, washing with cold ethanol, and carrying out vacuum drying at 50 ℃ for 8h to obtain the final product compound (benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base). Yield: 70 percent.
Nuclear magnetic analysis (nuclear magnetic spectrum is shown in figure 1) of the compound of the final product:
as shown in figure 1, the structural formula and nuclear magnetic resonance hydrogen spectrum analysis of the compound result in that the compound has 26 hydrogen in total. Wherein the signal peak (s,1H) appearing near 8.87ppm is the signal peak of proton 17 whose peak area is 1.00, and the signal peak (s,1H) appearing near 8.54ppm is the signal peak of proton 26 whose peak area is 1.03; the signal peak (s,1H) appearing in the vicinity of 7.93ppm was that of proton 22, and its peak area was 1.08; the signal peak (m,9H) appearing in the vicinity of 7.67ppm was that of proton 18, 20, 16, 19, 21, 23, 6, 7, 13, whose peak area was 8.92; the signal peak (p, J ═ 5.8Hz,2H) appearing around 7.31ppm was the signal peak for protons 15 and 24, and its peak area was 2.28; the signal peak (d, J ═ 7.3Hz,1H) appearing near 7.07ppm was that of proton 14, and its peak area was 1.06; the signal peak (s,2H) appearing in the vicinity of 6.35ppm was the signal peak of protons 3 and 10, the peak area of which was 2.16; the signal peak (d, J ═ 9.5Hz,2H) appearing around 6.21ppm was the signal peak for protons 5 and 10, and its peak area was 2.21; the signal peak (s,2H) appearing in the vicinity of 6.18ppm was the signal peak of protons 19 and 20, the peak area of which was 2.03; the signal peak (d, J ═ 5.3Hz,1H) appearing around 5.08ppm was the signal peak of proton 25, and its peak area was 1.45; the signal peaks (m,4H) appearing around 3.19 to 3.10ppm were those of protons 2 and 11, and the peak area thereof was 4.42; the signal peak (d, J ═ 9.1Hz,6H) appearing around 1.85ppm was the signal peak for protons 4 and 8, and its peak area was 6.27; the signal peak (t, J ═ 7.1Hz,6H) appearing around 1.20ppm was the signal peak for protons 1 and 12, and its peak area was 6.08. Therefore, the nuclear magnetic resonance hydrogen spectrogram of the compound well accords with the structure of the compound, namely benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base.
Application of iron ion fluorescent probe
Experimental example 1
Taking the benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base compound prepared in example 1, and reacting the compound with DMSO: dissolving in water (7/3v/v), diluting, and making into 1.0 × 10-5mol/L of sample solution. The fluorescence excitation wavelength of the compound was measured using an F-4600 fluorescence spectrophotometer, and the fluorescence spectrum of the compound was measured (the fluorescence spectrum was attached alone). Then adding equivalent amounts of different metal ions Hg into the solution respectively2+,Ag+,Mg2+, Cd2+,Al3+,Co2+,Ni2+,Cu2+,Zn2+,Cr2+And (2) measuring the fluorescence emission spectrum of the fluorescent probe molecule in the presence of each metal ion (as shown in figure 2), wherein after the iron ion is added, the probe molecule has a fluorescence peak at 575nm, the intensity is up to 1300, and no obvious emission peak is generated when other ions are added.
Claims (10)
1. A benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base is characterized in that: the structural formula is as follows:
2. the use of the benzimidazole benzaldehyde rhodamine hydrazine hydrate schiff base as described in claim 1, wherein: the method can be applied to the field of materials or sensors.
3. A process for preparing the benzimidazole benzaldehyde rhodamine hydrazine hydrate schiff base of claim 1, wherein: the method comprises the following specific steps:
1) weighing benzimidazole and anhydrous potassium carbonate, and dissolving in a solvent;
2) stirring the solution at a constant temperature of 60-120 ℃, adding p-fluorobenzaldehyde into the mixed solution, continuing to react for 10-25 h, cooling to room temperature, extracting with ethyl acetate, collecting supernatant, distilling under reduced pressure, separating by column chromatography, and drying in vacuum to obtain benzimidazole benzaldehyde;
3) weighing rhodamine 6G, and measuring hydrazine hydrate to dissolve in a solvent;
4) reacting the solution prepared in the step 3) for 6-15h under constant temperature stirring at 60-80 ℃, cooling to room temperature, performing suction filtration, recrystallizing, purifying, and drying in vacuum to obtain rhodamine hydrazine hydrate;
5) weighing the benzimidazole benzaldehyde obtained in the step 2) and the rhodamine hydrazine hydrate obtained in the step 4), dissolving in a solvent, adding glacial acetic acid, reacting at a constant temperature of 60-80 ℃ for 3-12 h, cooling to room temperature, crystallizing, filtering, and drying in vacuum to obtain a white powdery solid, namely a final product.
4. The method for preparing benzimidazole benzaldehyde rhodamine hydrazine hydrate schiff base according to claim 3, wherein the solvent in step 1), step 3) and step 5) is selected from N, N-dimethylformamide, dimethyl sulfoxide or ethanol.
5. The method for preparing benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base according to claim 3, wherein the molar ratio of benzimidazole to p-fluorobenzaldehyde in the step 2) is 1: 1-1: 2; the molar ratio of the benzimidazole to the solvent is 1: 10-1: 50.
6. The method for preparing benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base according to claim 3, wherein the molar ratio of rhodamine 6G and hydrazine hydrate in the step 3) is 1:1 to 1: 5.
7. The method for preparing the benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base as claimed in claim 3, wherein the molar ratio of the benzimidazole benzaldehyde rhodamine hydrazine hydrate in the step 5) is 1: 1-1: 3.
8. The method for preparing benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base according to claim 3, wherein the molar ratio of benzimidazole to anhydrous potassium carbonate is 1: 1-1: 3.
9. The method for preparing benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base as claimed in claim 3, wherein the molar ratio of rhodamine 6G to the solvent in the step 3) is 1: 10-1: 90.
10. The method for preparing benzimidazole benzaldehyde rhodamine hydrazine hydrate Schiff base as claimed in claim 7, wherein the molar ratio of glacial acetic acid to solvent is 1: 10-1: 100.
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