CN113512037A - Pyridopyrazinone ionic compound and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a pyridopyrazinone ionic compound and a preparation method and application thereof. The structural formula of the pyridopyrazinone ionic compound is shown as a formula (I), and the pyridopyrazinone ionic compound has excellent blue fluorescence and yellow-green fluorescence properties. Wherein the compound I-8 has specific response performance to different pH values and can be used as a pH probe for related field detection; meanwhile, the metal ion carrier has specific response to iron and aluminum metal ions.
Description
Technical Field
The invention belongs to the field of organic functional molecule research, and particularly relates to a pyridopyrazinone ionic compound, and a preparation method and application thereof.
Background
Organic compound fluorescent agents are widely applied to the fields of biological imaging, fluorescence sensors, food safety detection and the like. The practical application environment of the fluorescent agent is mostly carried out in an aqueous phase, and the problem of water solubility of the fluorescent agent exists. However, most organic compounds have very poor water solubility, which seriously affects the application of fluorescent agents in water. Therefore, the development of the water-soluble organic fluorescent agent has important significance, and the application scenes of the fluorescent agent can be widened. The problems of synthetic techniques need to be solved in order to obtain such compounds. Early researchers reported that a class of pyridopyrazinone ionic compounds was synthesized by reacting 2-pyridinecarboxamide or ethyl 2-picolinate with alpha-bromoethanones (J Heterocyclic Chem.,1990,27, 1673.). However, these synthetic methods only provide synthesis of the compounds of the examples, and the reaction time is long, and step-by-step reaction is required, and the literature does not report the fluorescence characteristics of the compounds.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims to provide a reaction technology for efficiently and simply synthesizing a pyridopyrazinone ionic compound as shown in formula (1), and solve the technical problem of long direct cyclization reaction time of 2-cyanopyridine and an alpha-bromoethanone compound.
Another object of the present invention is to provide a pyridopyrazinone ionic compound having fluorescent characteristics, such as pyridopyrazinone bromide represented by structural formula (I).
It is still another object of the present invention to provide use of the above pyridopyrazinone ionic compound.
The invention also provides a pyridopyrazinone ion compound having a specific response to pH and metal ions.
The purpose of the invention is realized by the following technical scheme:
a pyridopyrazinone bromide, the structural general formula of which is shown in formula (I):
in the formula (I), Ar is a benzene ring, a naphthalene ring, or an aromatic ring or an aromatic heterocyclic ring with a substituent;
the substituted aromatic ring is selected from benzene ring and naphthalene ring containing substituent:
the substituted aromatic heterocyclic ring is selected from the following classes:
(1) substituted benzoheterocycles: including coumarins, isoquinolines, imidazopyridines, indole rings, indazoles, benzothiophenes, and the like.
(2) Five-membered heterocyclic ring having substituent(s), for example: furan, thiophene, thiazole, pyrrole
Wherein R is1Selected from H, C1-C6Alkyl, halogen, C1-C6Alkoxy, hydroxy, ester, cyano;
R2selected from H, C1-C6Alkyl, halogen, C1-C6Alkoxy, hydroxy, ester, cyano;
said C1-C6Alkyl means a straight or branched chain alkyl group having 1 to 6 carbon atoms and may be, for example, but not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclohexyl, or longerLinear or branched alkyl groups of (a), and the like.
Said C1-C6Alkoxy means C as defined above1-C6A group in which an alkyl group is bonded to an O atom.
The halogen means a halogen element, and may be, for example, F, Cl, Br or I, without limitation.
Preferably, the pyridopyrazinone bromide is a compound represented by the following structural formula:
in order to develop a novel preparation technology and obtain the compound, the inventor carries out intensive research, and after a great deal of creative work, the inventor finds that under the catalysis of a nickel salt system, 2-cyanopyridine and alpha-bromoethanone compounds can be directly cyclized to synthesize the pyridopyrazinone bromide in one step. The method has the advantages of easily obtained raw materials, simple operation, compatibility with various heterocycles or functional groups and moderate to excellent yield, and is a method for efficiently preparing the pyridopyrazinone.
The method for efficiently preparing the pyridopyrazinone comprises the following steps: in the presence of nickel salt, reacting a compound II with alpha-bromoethyl ketone (compound III) in a solvent to prepare pyridopyrazinone bromide shown in a formula I; the synthetic route is shown as formula (1):
in the formula (II) wherein R is a substituent1Preferred ranges of the aromatic ring Ar are as described above.
According to the synthesis method disclosed by the invention, the molar ratio of the compound II to the alpha-bromoethanone is 1:1-4, but the molar ratio can be 1:1, 1:1.2, 1:1.5, 1:2.0, 1:3.0 or 1: 4.0.
In the synthesis method of the present invention, the molar ratio of the compound ii to the nickel salt is 1:0.05 to 2, but not limited to, 1:0.05, 1:0.1, 1:0.5, 1:1, and 1:2.
According to the synthesis method, the nickel salt is more than one of nickel chloride, nickel fluoride, nickel bromide or nickel sulfate.
The reaction solvent in the reaction of compound ii and compound iii in the synthesis method of the present invention is an organic solvent or a mixed solvent of an organic solvent and water, and may be, for example, but not limited to, any one or more of acetonitrile, a mixed solvent of acetonitrile and water, a mixed solvent of N, N-Dimethylformamide (DMF) and water, a mixed solvent of ethanol and water, a mixed solvent of dimethyl sulfoxide (DMSO) and water, a mixed solvent of tetrahydrofuran and water, N-Dimethylformamide (DMF), ethanol, methanol, dimethyl sulfoxide (DMSO), tetrahydrofuran, N-propanol, isopropanol, butanol, pentanol, acetone, 2-butanone, and the like, and most preferably, a mixed solvent of acetonitrile and water.
In the synthesis method of the present invention, the volume ratio of the mixed solvent of acetonitrile and water is 1:0 to 2, but not limited to, 1:0, 1:0.1, 1:0.5, 1:1, 1:2.
In the synthesis method of the present invention, the reaction temperature is 100 ℃ and 140 ℃, but not limited to, 100 ℃, 120 ℃, 130 ℃, 140 ℃.
In the synthesis method of the present invention, any conventional treatment means known in the field of organic synthesis, for example, any one treatment means or a combination of a plurality of treatment means in crystallization, column chromatography purification, extraction, and the like, may be used for the post-treatment after the completion of the reaction. As an exemplary post-processing means, for example, there may be: after the reaction is finished, removing the solvent from the mixture obtained after the reaction is finished by using a rotary evaporator, purifying the residue by using a 300-400-mesh silica gel column chromatography to obtain a target product, and determining a proper elution end point by using TLC (thin layer chromatography) for tracking and monitoring.
The pyridopyrazinone bromide is obtained in one step by using 2-cyanopyridine and alpha-bromoethyl ketone compound as raw material, nickel salt as catalyst and proper selection and combination of other technological parameters.
The compound I has excellent blue fluorescence and yellow-green fluorescence properties, so that the compound I can be applied to preparation of fluorescent materials.
Fluorescent compound I-8 sensitive to pH value
The fluorescence of the fluorescent compound I-8 changes under the change of the pH of the solution, the maximum emission wavelength of a fluorescent color developing agent (the fluorescent compound I-8) in the solution changes when the pH is reduced, the fluorescence color changes from green to blue when the pH is reduced under the irradiation of a 365nm ultraviolet lamp, the color change interval is 3.5-4.9, and the fluorescent compound I-8 can be applied to the acidity detection of an organic acid aqueous solution and the acidity detection of a metal ion aqueous solution.
The fluorescent compound I-8 has a unique response color change interval of pH 3.5-4.9, and simultaneously has specific response to iron and aluminum metal ions. Therefore, the probe can be used as a pH probe for related field detection, can be used for detecting plant endogenous acids such as salicylic acid, nicotinic acid and the like, and is not influenced by amino acid; or for specific detection of Fe3+And Al3+Ions.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the preparation method has the advantages of short reaction time, cheap and easily-obtained raw materials, high product yield, high purity and the like, provides an effective synthesis method for preparing the novel pyridopyrazinone compound, and has good research value and application prospect. The method finds a pyridopyrazinone structure with a unique response to pH, provides application, development and research of the pyridopyrazinone structure with the unique response to pH, determines the relation between the fluorescence change of the compound I-8 in a solution and the pH value, and provides examples of pH value detection of an organic acid aqueous solution and detection of metal ions.
Drawings
FIG. 1 shows the results of fluorescence measurement of 100. mu.M methanol solutions of compounds I-1 to I-12 in example 3.
FIG. 2 is a fluorescence emission spectrum of 10. mu.M samples of example 4 in 100mM sodium dihydrogenphosphate-disodium hydrogenphosphate buffer solution buffer solvent at different pH.
FIG. 3 is a graph showing the maximum fluorescence intensity of 10. mu.M samples in example 4 in sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solutions buffer solvents at different pH values.
FIG. 4 is the maximum emission wavelength of 10 μ M samples in sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solutions buffer solvents at different pH's in example 4.
FIG. 5 shows the maximum emission wavelength of 10. mu.M samples in different concentrations of an aqueous organic acid in example 5.
FIG. 6 shows the maximum emission wavelength of fluorescence of 10 μ M samples in solutions of different concentrations of metal ions in example 6.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The reaction solvent used in example 1-2 was a mixed solvent of acetonitrile and water in a volume ratio of 1: 0-2.
Example 1 Synthesis of 1-oxo-3-phenyl-1, 2-dihydropyridine [1,2-a ] pyrazine-5-ammonium bromide (I-1).
The synthetic route is as follows:
the method specifically comprises the following steps:
the compound (II-1) of the above formula, the compound (III-1) and nickel chloride were mixed in a molar ratio of 1:1.5:0.5, wherein the compound of the formula (II-1) was 2 mmol. The reaction was stirred at 140 ℃ for 12 hours. And cooling after the reaction is finished, carrying out rotary evaporation on the reaction system, removing the solvent, carrying out silica gel column chromatography on the residue, eluting the residue with dichloromethane-methanol at a ratio of 10:1, detecting by TLC, combining effluent containing the product, distilling by using a rotary evaporator to remove the solvent, and carrying out vacuum drying to obtain the target product of a yellow solid, wherein the yield is 79%, and the purity is 99.4% (HPLC).
The detection data of the hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the infrared spectrum of the compound I-1 prepared in the example are as follows:
1H NMR(600MHz,DMSO-d6)δ13.13(s,1H),9.55–9.37(m,1H),8.83–8.66(m,2H),8.64(t,J＝8.1Hz,1H),8.46(t,J＝7.1Hz,1H),7.91–7.82(m,2H),7.66–7.55(m,3H).
13C NMR(151MHz,DMSO)δ156.8,142.4,139.0,138.3,138.1,131.9,130.4,129.9,129.7,127.8,126.7,110.5.
example 2.8- (Methoxycarbonyl) -1-oxo-3-phenyl-1, 2-dihydropyridine [1,2-a ] pyrazine-5-ammonium bromide (I-8) synthesis.
The synthetic route is as follows:
the method specifically comprises the following steps:
the compound (II-8) of the above formula, the raw material (III-8) and nickel chloride were mixed in a molar ratio of 1:1.5:0.5, wherein the compound of the formula (II-8) was 2 mmol. The reaction was stirred at 140 ℃ for 12 hours. And cooling after the reaction is finished, carrying out rotary evaporation on the reaction system, removing the solvent, carrying out silica gel column chromatography on the residue, eluting the residue with dichloromethane-methanol at a ratio of 10:1, detecting by TLC, combining effluent liquid containing the product, distilling by using a rotary evaporator to remove the solvent, and carrying out vacuum drying to obtain the target product of yellow solid, wherein the yield is 13%, and the purity is 99.5% (HPLC).
The data of the hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and infrared spectrum of the compound (I-8) obtained in this example were as follows:
1H NMR(600MHz,TFA)δ9.48(s,1H),9.22(d,J＝6.6Hz,1H),8.79(d,J＝6.5Hz,1H),8.25(s,1H),7.74(d,J＝7.6Hz,2H),7.66(t,J＝7.5Hz,1H),7.59(t,J＝7.7Hz,2H),4.16(s,3H).
13C NMR(151MHz,TFA)δ165.3,159.4,144.3,143.2,141.7,138.5,135.8,133.3,132.3,130.3,129.2,128.7,113.4,57.8.
example 3: the invention records the fluorescence spectrograms of different 100 mu M compound (I-1-I-12) methanol solutions as shown in figure 1, and Table 1 shows the test parameters of a fluorescence spectrometer. The results show that the compound I can be used as a blue and yellow-green fluorescent material.
TABLE 1 fluorescence Spectroscopy test parameters
The invention also screens out a pyridopyrazinone structure (I-8) which has unique response to pH, and provides application, development and research of the pyridopyrazinone with specific properties.
Example 4: application development studies in which compound I-8 responds uniquely to pH.
Weighing 18mg of the compound I-8, and dissolving the compound I-8 in 1L of deionized water to prepare 50 mu M of compound I-8 aqueous solution A; preparing 100mM sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solutions with different pH values of 7.0, 6.0, 4.9, 4.1, 3.5, 3.1 and 2.0 as solution B;
fluorescence emission spectra of 10 μ M samples in 100mM sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solutions at different pH: mixing the solution A and the solution B in a volume ratio of 1:4, shaking for 1min to prepare a solution C, measuring the fluorescence emission spectrum of the solution C by using a fluorescence spectrometer, and taking the table 2 as the test parameters of the fluorescence spectrometer.
The results are shown in FIGS. 2, 3 and 4. The compound I-8 has unique response to pH, and when the pH value of the sodium dihydrogen phosphate-disodium hydrogen phosphate buffer solution is reduced, the maximum excitation light intensity of the compound I-8 at the wavelength of 430nm is firstly increased and then gradually reduced, and the fluorescence of the compound is changed from green to blue. When the pH is 7.0-4.9, the maximum emission wavelength of the compound I-8 at the wavelength of 430nm is more than 500, and the fluorescence of the compound is green; the maximum emission wavelength of compound I-8 began to decrease significantly as the pH decreased to 4.9, and the fluorescence of compound I-8 began to change from green to bluish blue, while the maximum emission wavelength of compound I-8 at a wavelength of 430nm was less than 485nm and completely changed to blue as the pH decreased to 3.5.
TABLE 2 fluorescence Spectroscopy test parameters
Example 5
To verify the response of compound I-8 to the acidity of organic acids, the response of compound I-8 to various concentrations of glycine, L-cysteine, salicylic acid, nicotinic acid, acetic acid in aqueous solution is provided:
weighing 7.2mg of the compound I-8, and dissolving in 1L of deionized water to prepare a 20 mu M compound I-8 aqueous solution D; preparing deionized water solutions of glycine, L-cysteine, salicylic acid, nicotinic acid and acetic acid with the concentrations of 0,2 mu M, 20 mu M and 200 mu M respectively as a solution E;
fluorescence emission spectra of 10 μ M samples in different concentrations of glycine, L-cysteine, salicylic acid, nicotinic acid, acetic acid: and mixing the solution D and the solution E in a volume ratio of 1:1, oscillating for 1min to prepare a solution F, and measuring the fluorescence emission spectrum of the solution F by using a fluorescence spectrometer, wherein the measurement parameters of the fluorescence spectrometer are shown in Table 3.
The results are shown in FIG. 5. The amino acids are amphoteric substances, the pKa of salicylic acid is 2.98, the pKa of nicotinic acid is 4.85, and the pKa of acetic acid is 4.74, and the ordering of the amino acids at the pH of an aqueous solution is that salicylic acid > acetic acid > nicotinic acid > glycine > L-cysteine. When the concentrations of salicylic acid, acetic acid and nicotinic acid as organic acid are increased, the maximum emission wavelength of the compound I-8 is in a descending trend at an excitation wavelength of 430nm, when the concentration is more than or equal to 100 mu M, the fluorescence is converted from green to bluish blue, and the descending trend is that the salicylic acid is more than the acetic acid and is more than the nicotinic acid; when the concentration of the organic acid glycine/L-cysteine is increased, the maximum emission wavelength of the compound I-8 is not obviously changed under the excitation wavelength of 430nm, and the experimental result accords with the theory.
TABLE 3 fluorescence Spectroscopy test parameters
Example 6
In order to verify the response of the compound I-8 to the acidity of metal ion solutions with different concentrations, the compound I-8 is provided for NaCl and MgSO with different concentrations4、AlCl3、Zn(NO3)2、FeBr3、CuCl2、CaCl2Response of aqueous solution:
experimental procedures referring to example 4, the fluorescence spectrometer test parameters are given in Table 4.
The results are shown in FIG. 6. Mg (OH)2、Al(OH)3、Zn(OH)2、Fe(OH)3、Cu(OH)2、Ca(OH)2K ofspAre respectively 1.8 multiplied by 10-11、1.3×10-33、7.1×10-18、3.2×10-38、5.0×10-20、5.5×10-6。NaCl、MgSO4、AlCl3、Zn(NO3)2、FeBr3、CuCl2、CaCl2The pH sequence of the aqueous solution is FeBr under the same concentration3>AlCl3>CuCl2>Zn(NO3)2>MgSO4>CaCl2>And (5) NaCl. When the concentration of the metal ions is 1mM, FeBr can be calculated3、AlCl3、CuCl2The pH of the solution was 2.5, 4.0, 5.7, respectively. When FeBr3、AlCl3When the concentration is increased, the maximum emission wavelength of the compound I-8 is in a descending trend at the excitation wavelength of 430nm, and when the concentration is more than or equal to 100 mu M, the fluorescence is converted from green to bluish, and the descending trend is FeBr3>AlCl3(ii) a When CuCl is present2、Zn(NO3)2、MgSO4、CaCl2When the NaCl concentration is increased, the maximum emission wavelength of the compound I-8 has no obvious change under the excitation wavelength of 430nm, and the experimental result accords with the theory.
TABLE 4 fluorescence Spectroscopy test parameters
| Excitation wavelength | 430.0nm |
| Scanning start wavelength | 440.0nm |
| End of scan wavelength | 830.0nm |
| EX slit width | 2.5nm |
| Width of EM slit | 2.5nm |
| PMT Voltage | 600V |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A pyridopyrazinone ionic compound is characterized in that the structural general formula is shown as formula (I):
in the formula (I), Ar is a benzene ring, a naphthalene ring, or an aromatic ring or an aromatic heterocyclic ring with a substituent;
the substituted aromatic ring is selected from the following structures:
the substituted aromatic heterocyclic ring is selected from the following classes:
(1) substituted benzoheterocycles:
(2) five-membered heterocycle with substituents:
wherein R is1Selected from H, C1-C6Alkyl, halogen, C1-C6Alkoxy, hydroxy, ester, cyano;
R2selected from H, C1-C6Alkyl, halogen, C1-C6Alkoxy, hydroxyl, ester group and cyano.
2. The pyridopyrazinone ionic compound according to claim 1, wherein said pyridopyrazinone ionic compound is represented by the following structural formula:
3. a process for producing a pyridopyrazinone ionic compound according to claim 1 or 2, comprising the steps of: in the presence of nickel salt, reacting a compound II with corresponding alpha-bromoethyl ketone in a reaction solvent to prepare a pyridopyrazinone ionic compound shown in a formula I; the synthetic route is shown as formula (1):
in the formula (I), Ar is a benzene ring, a naphthalene ring, or an aromatic ring or an aromatic heterocyclic ring with a substituent;
the substituted aromatic ring is selected from the following structures:
the substituted aromatic heterocyclic ring is selected from the following classes:
(1) substituted benzoheterocycles:
(2) five-membered heterocycle with substituents:
wherein R is1Selected from H, C1-C6Alkyl, halogen, C1-C6Alkoxy, hydroxy, ester, cyano;
R2selected from H, C1-C6Alkyl, halogen, C1-C6Alkoxy, hydroxyl, ester group and cyano.
4. The method for producing a pyridopyrazinone ionic compound according to claim 3, wherein the molar ratio of the compound ii to the alpha-bromoethanone is 1: 1-4; the molar ratio of the compound II to the nickel salt is 1: 0.05-2.
5. The method for producing a pyridopyrazinone ionic compound according to claim 3, wherein the nickel salt is one or more of nickel chloride, nickel fluoride, nickel bromide, or nickel sulfate.
6. The method for preparing a pyridopyrazinone ionic compound according to claim 3, wherein the reaction temperature is 100-140 ℃.
7. The process for producing a pyridopyrazinone ionic compound according to claim 3, wherein the reaction is carried out in an organic solvent or a mixed solvent of an organic solvent and water, preferably a mixture of acetonitrile and water, in a volume ratio of 1:0 to 2.
8. Use of a pyridopyrazinone ionic compound according to claim 1 or 2 as a fluorescent material.
9. Use of a fluorescent compound I-8, characterized in that:
the structural formula of the fluorescent compound I-8 is
It is applied to pH probe or used for specific detection of Fe3+And Al3+Ions.
10. Use according to claim 9, characterized in that: the fluorescent compound I-8 is applied to detection of plant endogenous acid, detection of acidity of organic acid aqueous solution and detection of acidity of metal ion aqueous solution.
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| CN103323415A (en) * | 2013-07-01 | 2013-09-25 | 广州市酒类检测中心 | Enzyme inhibition method for detecting carbamates |
| CN106008501A (en) * | 2016-06-20 | 2016-10-12 | 武汉大学 | Bipolar compound containing pyridopyrazine unit and preparation method and application of compound |
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2021
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| CN103323415A (en) * | 2013-07-01 | 2013-09-25 | 广州市酒类检测中心 | Enzyme inhibition method for detecting carbamates |
| CN106008501A (en) * | 2016-06-20 | 2016-10-12 | 武汉大学 | Bipolar compound containing pyridopyrazine unit and preparation method and application of compound |
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| FRITZ KROEHNKE等: "Syntheses of 1-hydroxydehydroquinolizinium and oxa- and azadehydroquinolizinium salts", 《CHEMISCHE BERICHTE》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248493A (en) * | 2021-03-22 | 2021-08-13 | 广州汇标检测技术中心 | Fluorescent agent and method for rapidly and visually detecting carbamate pesticide residues |
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| CN113512037B (en) | 2022-12-09 |
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