CN116143775A - Fluorescent material synthesis method for rapidly detecting sulfur content - Google Patents
Fluorescent material synthesis method for rapidly detecting sulfur content Download PDFInfo
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- indolizine
- bishydrazide
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 43
- 239000011593 sulfur Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 8
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 32
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical class CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 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 abstract description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011973 solid acid Substances 0.000 claims abstract description 13
- HOBCFUWDNJPFHB-UHFFFAOYSA-N indolizine Chemical compound C1=CC=CN2C=CC=C21 HOBCFUWDNJPFHB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000003222 pyridines Chemical class 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 150000002478 indolizines Chemical class 0.000 claims description 19
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 claims description 16
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 11
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 8
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 7
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 claims description 4
- 238000012824 chemical production Methods 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 238000012921 fluorescence analysis Methods 0.000 claims description 2
- 238000001917 fluorescence detection Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 4
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000007850 fluorescent dye Substances 0.000 abstract description 17
- 238000001514 detection method Methods 0.000 abstract description 11
- 238000010992 reflux Methods 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 4
- 125000000623 heterocyclic group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 239000012295 chemical reaction liquid Substances 0.000 description 18
- 238000001914 filtration Methods 0.000 description 14
- 238000001953 recrystallisation Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003068 molecular probe Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/04—Ortho-condensed systems
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
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- Health & Medical Sciences (AREA)
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- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
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Abstract
The invention relates to a method for synthesizing a fluorescent material for rapidly detecting sulfur content, which comprises the steps of controlling certain reaction conditions by adopting pyridine derivatives, halogenated ethyl acetate and methyl acrylate under the action of a solid acid catalyst, obtaining indolizine serving as a fluorescent parent body containing a heterocyclic structure in one step, and obtaining a bishydrazide indolizine fluorescent probe after refluxing with hydrazine hydrate. The synthesis method can solve the problems of complex operation, long reaction time, large solvent consumption, low yield and the like of the traditional route. The fluorescent probe is applied to detection of trace sulfur in nitrochlorobenzene, and has the characteristics of high selectivity, high sensitivity, short response time, low detection limit, strong anti-interference capability and the like.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and relates to a method for synthesizing a fluorescent material for rapidly detecting sulfur content, in particular to a method for synthesizing a fluorescent probe for rapidly detecting sulfur content in nitrochlorobenzene.
Background
Nitrochlorobenzene is a basic chemical raw material, the derivative products of the nitrochlorobenzene reach hundreds of kinds, and the nitrochlorobenzene is widely applied to industries such as dye intermediates, rubber additives and the like. The nitrochlorobenzene produced in industry is often provided with a small amount of thiophene, benzothiophene and other derivatives, and the sulfides not only affect the purity of the product, but also affect the production of downstream products, in particular to the catalyst of hydrogenation and other processes; meanwhile, the sulfur-containing compound is discharged in the processing of the large-tonnage nitrochlorobenzene products, and the environmental protection requirement on the device is high. At present, the sulfur content in the product is usually detected by adopting a microcoulomb method, an ultraviolet fluorescence method, an inductively coupled plasma method and the like, each method has the advantages of thousands of years, narrow application range, poor sensitivity and interference resistance, easiness in being interfered by elements such as nitrogen, chlorine and the like, and difficulty in accurately and efficiently measuring the actual content.
The fluorescent molecular probe is widely applied to chemical industry, biology, medicine and environmental monitoring, indolizine is taken as an important fluorescent chromophore, people are widely concerned in the field of fluorescent probes, and according to literature reports, indolizine derivatives are mainly concentrated on the recognition effect on metal ions, and are less applied in the field of chemical production.
Chinese patents CN 106632406B, CN106010508B, CN103980885B, CN109749734a, etc. all relate to the preparation of indolizine derivatives and the behavior of fluorescent probes, but the cyclization reaction of indolizine precursors is basically synthesized by two steps: firstly, dissolving pyridine derivative and halogenated ethyl acetate in a solvent, stirring at normal temperature for 5-6 h to gradually precipitate, and filtering out the precipitate to obtain pyridine onium salt. And then, dissolving onium salt and methyl acrylate in DMF, reacting for 4-6 hours at a certain temperature, pouring the materials into dilute hydrochloric acid after the reaction is finished to obtain crude indolizine compounds, and obtaining pure products through post-treatment procedures such as dissolving, filtering, washing, extracting, column chromatography and the like. The preparation method has the advantages of long reaction time, large solvent consumption, complex operation and low yield.
Disclosure of Invention
The invention provides a method for synthesizing a fluorescent material for rapidly detecting sulfur content, in particular to a method for synthesizing a bishydrazide indolizine fluorescent probe for rapidly detecting trace sulfur in nitrochlorobenzene.
The main technical scheme of the invention is as follows: the method for synthesizing the fluorescent material for rapidly detecting the sulfur content is characterized in that pyridine derivatives, halogenated ethyl acetate and methyl acrylate are adopted to react under the action of a solid acid catalyst, indolizine in a fluorescent chromophore is obtained in one step, and then the obtained product is refluxed with hydrazine hydrate to obtain the bishydrazide indolizine derivatives.
Preferably, the pyridine derivative is selected from pyridine, 2-picoline or 3-picoline, preferably 3-picoline.
Preferably, the halide is selected from ethyl bromoacetate, ethyl fluoroacetate, ethyl chloroacetate, preferably ethyl bromoacetate.
Preferably, the solid acid catalyst is SO 4 2- /ZrO 2 。
Preferably, the molar ratio of the pyridine derivative to the methyl acrylate is 1:1 to 3.3, preferably 1:1 to 2.8.
Preferably, the reaction temperature is 40-100 ℃, and the reaction time is 2-8 hours.
The bishydrazide indolizine derivative synthesized by the invention can be used in the field of fluorescence analysis or detection in chemical production, and is particularly used for rapidly detecting trace sulfur in nitrochlorobenzene.
The invention takes pyridine derivative, halogenated ethyl acetate and methyl acrylate as raw materials, adds solid acid catalyst, reacts under certain condition, obtains nitrogen heterocyclic fluorescent parent indolizine by one-step method, and then returns with hydrazine hydrate to obtain crude product of bishydrazide indolizine derivative, and pure product can be obtained after filtration and recrystallization, and the total yield reaches more than 60%.
Compared with the traditional process, the synthesis method has the advantages of remarkable improvement, high yield, short reaction time, simple operation, less solvent consumption and the like. The bishydrazide indolizine derivative can quickly coordinate with sulfur to form a complex with a specific structure, induces obvious change of fluorescence spectrum, has no response to other common metal ions, chlorine, nitrogen and other nonmetallic elements, and can be used as a sulfur fluorescence probe with excellent performance. The probe is used for measuring trace sulfur in nitrochlorobenzene production, and has the advantages of high selectivity, short response time, high sensitivity, strong anti-interference capability and the like.
The indolizine fluorescent chromophore is synthesized by adopting a one-step method, and the obtained fluorescent probe has the advantages of high selectivity, short response time, high sensitivity, strong anti-interference capability, convenience for real-time in-situ and remote detection and the like, and can rapidly and accurately detect the trace sulfur content in nitrochlorobenzene.
Detailed Description
The present invention will be described in detail with reference to specific examples. It should be noted that these examples are not intended to limit the scope of the invention, which is defined by the appended claims.
Thiophene with different proportions is respectively added into nitrochlorobenzene, and the sulfur content of the nitrochlorobenzene is detected by a bishydrazide indolizine fluorescent probe. The test result shows that the sulfur can cause the fluorescence spectrum to change obviously, the fluorescence intensity is reduced continuously along with the increase of the sulfur content, and the fluorescence intensity shows good linear relation in a wider concentration range, and the detection limit reaches ppm level; in addition, the fluorescence emission peak has a certain red shift, so that sulfur in the nitrochlorobenzene product can be rapidly and efficiently identified.
To verify the selectivity and anti-interference capability of the fluorescent probe, selectingCommon metal ion (Cu is selected) 2+ ，Zn 2+ ，Al 3 + ，Ni 2+ ，Li + ，Cd 2+ ，Ba 2+ ，Mn 2+ ，Co 2+ ，Ca 2+ ，Cr 3+ ，Ag + ，Fe 3+ ，Pb 2+ ，Mg 2+ ，Hg 2+ 16 common ions, such as non-metal ions (Cl) - 、NO 3 - ) Experiments show that the bishydrazide indolizine fluorescent probe has no obvious response to the ions and has high selectivity and anti-interference force.
Example 1
1mol of pyridine and 1mol of ethyl bromoacetate are dissolved in 30ml of DMF and 1.5g of SO are added 4 2- /ZrO 2 1mol of methyl acrylate is dripped into the solid acid catalyst, the reaction is carried out for 8 hours at the temperature of 40 ℃, then a proper amount of hydrazine hydrate is added into the reaction liquid for reflux, the reaction liquid is naturally cooled after the reaction is finished, a large amount of solids are separated out, and the pure product of bishydrazide indolizine derivative can be obtained after filtration and recrystallization, and the yield is 61.3 percent. The product is used for fluorescent probes to detect trace sulfur in nitrochlorobenzene, sulfur can be detected in a wider concentration range, the sensitivity is high, the fluorescent intensity and the concentration of sulfur are in a good linear relation, the linear equation is if= 654.14-13.396C, C is the concentration of sulfur, the unit is mg/L, the correlation coefficient R= -0.9996, and the detection limit is 0.7mg/L.
Example 2
1mol of 2-methylpyridine, 1mol of ethyl chloroacetate are dissolved in 30ml of DMF and 2.5g of SO are added 4 2- /ZrO 2 1.6mol of methyl acrylate is dripped into the solid acid catalyst, the reaction is carried out for 5 hours at the temperature of 80 ℃, then a proper amount of hydrazine hydrate is added into the reaction liquid for reflux, the reaction liquid is naturally cooled after the reaction is finished, a large amount of solids are separated out, and the pure product of bishydrazide indolizine derivative can be obtained after filtration and recrystallization, and the yield is 60.0%. The product is used for fluorescent probes to detect trace sulfur in nitrochlorobenzene, sulfur can be detected in a wider concentration range, the sensitivity is high, the fluorescence intensity and the concentration of sulfur are in good linear relation, the linear equation is if= 611.55-11.315C, C is the concentration of sulfur, the unit is mg/L, the correlation coefficient R= -0.9996, and the detection limit is high0.4mg/L.
Example 3
1mol of 3-methylpyridine, 1mol of ethyl chloroacetate are dissolved in 30ml of DMF and 2g of SO are added 4 2- /ZrO 2 2.8mol of methyl acrylate is dripped into the solid acid catalyst, the reaction is carried out for 3 hours at the temperature of 100 ℃, then a proper amount of hydrazine hydrate is added into the reaction liquid for reflux, the reaction liquid is naturally cooled after the reaction is finished, a large amount of solids are separated out, and the pure product of bishydrazide indolizine derivative can be obtained after filtration and recrystallization, and the yield is 61.3 percent. The product is used for fluorescent probes to detect trace sulfur in nitrochlorobenzene, sulfur can be detected in a wider concentration range, the sensitivity is high, the fluorescent intensity and the concentration of sulfur are in a good linear relation, the linear equation is if= 690.17-15.2912, C is the concentration of sulfur, the unit is mg/L, the correlation coefficient R= -0.9997, and the detection limit is 0.1mg/L.
Example 4
1mol of pyridine, 1mol of ethyl fluoroacetate are dissolved in 30ml of DMF and 2.2g of SO are added 4 2- /ZrO 2 2.5mol of methyl acrylate is dripped into the solid acid catalyst, the reaction is carried out for 6 hours at 50 ℃, then a proper amount of hydrazine hydrate is added into the reaction liquid for reflux, the reaction liquid is naturally cooled after the reaction is finished, a large amount of solids are separated out, and the pure product of bishydrazide indolizine derivatives can be obtained after filtration and recrystallization, and the yield is 60.6%. The product is used as a fluorescent probe to detect trace sulfur in nitrochlorobenzene, and the application effect is the same as that of example 1.
Example 5
1mol of 2-methylpyridine, 1mol of ethyl chloroacetate are dissolved in 50ml of DMF and 2g of SO are added 4 2- /ZrO 2 2mol of methyl acrylate is dripped into the solid acid catalyst, the reaction is carried out for 5 hours at the temperature of 75 ℃, then a proper amount of hydrazine hydrate is added into the reaction liquid for reflux, the reaction liquid is naturally cooled after the reaction is finished, a large amount of solids are separated out, and the pure product of bishydrazide indolizine derivative can be obtained after filtration and recrystallization, and the yield is 63.7%. The product is used as a fluorescent probe to detect trace sulfur in nitrochlorobenzene, and the application effect is the same as that of example 2.
Example 6
1mol of 3-methylpyridine, 1mol of ethyl chloroacetate are dissolved in 40ml of DMF and 2.2g of SO are added 4 2- /ZrO 2 3.3mol of methyl acrylate is dripped into the solid acid catalyst, the reaction is carried out for 3 hours at the temperature of 85 ℃, then a proper amount of hydrazine hydrate is added into the reaction liquid for reflux, the reaction liquid is naturally cooled after the reaction is finished, a large amount of solids are separated out, and the pure product of bishydrazide indolizine derivative can be obtained after filtration and recrystallization, and the yield is 64.8%. The product is used in the field of fluorescent probes, trace sulfur in nitrochlorobenzene is detected, and the application effect is the same as that of example 3.
Example 7
1mol of 3-pyridine, 1mol of ethyl fluoroacetate are dissolved in 30ml of DMF and 2.6g of SO are added 4 2- /ZrO 2 1.5mol of methyl acrylate is dripped into the solid acid catalyst, the reaction is carried out for 5.5 hours at the temperature of 60 ℃, then a proper amount of hydrazine hydrate is added into the reaction liquid for reflux, the reaction liquid is naturally cooled after the reaction is finished, a large amount of solids are separated out, and the bishydrazide indolizine derivative pure product can be obtained after filtration and recrystallization, and the yield is 61.2%. The product is used in the field of fluorescent probes, trace sulfur in nitrochlorobenzene is detected, and the application effect is the same as that of example 3.
Comparative example 1
1mol of 3-methylpyridine is dissolved in ethyl acetate, 1mol of ethyl bromoacetate is added, 4. 4 h is stirred, the precipitate is filtered off, the solid is washed with a small amount of ethyl acetate and air-dried for later use. 0.5mol of onium salt is weighed and dissolved in 20ml of DMF, 5ml of triethylamine and 2mol of methyl acrylate are added for reaction for 6 hours at 100 ℃, the reaction liquid is poured into 100ml of 5% dilute hydrochloric acid, the precipitation of earth color is separated out, the filtration is carried out, the precipitation is separated out, the reaction liquid and hydrazine hydrate are cooled after refluxing, and the bishydrazide indolizine derivative is obtained after filtration and recrystallization, and the total product yield is 28.7%.
Comparative example 2
1mol of 3-methylpyridine is dissolved in ethyl acetate, 1mol of ethyl chloroacetate is added, 5.5h is stirred, the precipitate is filtered off, and the solid is washed with a small amount of ethyl acetate and air-dried for later use. 0.5mol of onium salt is weighed and dissolved in 30ml of DMF, 5ml of triethylamine and 1.5mol of methyl acrylate are added for reaction for 8 hours at 60 ℃, the reaction liquid is poured into 100ml of 5% dilute hydrochloric acid, the precipitation of earth color is separated out, the filtration is carried out, the precipitation is separated out, the reaction liquid and hydrazine hydrate are cooled after refluxing, and the bishydrazide indolizine derivative is obtained after filtration and recrystallization, wherein the total product yield is only 25.3%. .
Comparative example 3
The sulfur content in nitrochlorobenzene is measured by microcoulomb method, the detection limit is 20 mg/L, and the detection result is easy to be interfered by chlorine, nitrogen and other elements, so that the error of the detection result is larger. When the inductively coupled plasma method is used for measurement, a part of sulfur is lost in the excited state process, and the method is interfered by trace sulfur in the surrounding environment, so that errors are caused to sulfur detection, and the method is not suitable for detecting trace sulfur in nitrochlorobenzene products.
Claims (10)
1. A method for synthesizing fluorescent material for quickly detecting sulfur content is characterized in that pyridine derivative, halogenated ethyl acetate and methyl acrylate are adopted to react under the action of solid acid catalyst, indolizine in fluorescent chromophore is obtained in one step, and then the obtained product is refluxed with hydrazine hydrate to obtain bishydrazide indolizine derivative.
2. The synthetic method according to claim 1, characterized in that the pyridine derivative is selected from pyridine, 2-picoline or 3-picoline.
3. The synthetic method according to claim 2, characterized in that the pyridine derivative is 3-methylpyridine.
4. The synthetic method according to claim 1, wherein the halide is selected from the group consisting of ethyl bromoacetate, ethyl fluoroacetate, ethyl chloroacetate.
5. The method of claim 4, wherein the halide is ethyl bromoacetate.
6. The method of synthesis according to claim 1, wherein the solid acid catalyst is SO 4 2- /ZrO 2 。
7. The synthetic method according to claim 1, wherein the molar ratio of the pyridine derivative to the methyl acrylate is 1:1 to 3.3, preferably 1:1 to 2.8.
8. The synthesis method according to claim 1, wherein the reaction temperature is 40-100 ℃ and the reaction time is 2-8 hours.
9. The synthesis method according to claim 1, wherein the bishydrazide indolizine derivative is used in the field of fluorescence analysis or detection in chemical production.
10. The synthesis method according to claim 9, wherein the bishydrazide indolizine derivative is used for rapidly detecting trace sulfur in nitrochlorobenzene.
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| CN202111375806.5A CN116143775A (en) | 2021-11-19 | 2021-11-19 | Fluorescent material synthesis method for rapidly detecting sulfur content |
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