CN116283968A - Acetamido imidazopyridine compound and preparation method and application thereof - Google Patents
Acetamido imidazopyridine compound and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- -1 Acetamido imidazopyridine compound Chemical class 0.000 title abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 17
- 235000012736 patent blue V Nutrition 0.000 claims abstract description 11
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000012632 fluorescent imaging Methods 0.000 claims abstract description 6
- 239000000990 laser dye Substances 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- 229940125890 compound Ia Drugs 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- KHVZPFKJBLTYCC-UHFFFAOYSA-N (2-amino-5-bromophenyl)-pyridin-2-ylmethanone Chemical compound NC1=CC=C(Br)C=C1C(=O)C1=CC=CC=N1 KHVZPFKJBLTYCC-UHFFFAOYSA-N 0.000 claims description 8
- ZWFMOGMVCCFQRG-UHFFFAOYSA-N n-(1h-imidazo[4,5-b]pyridin-2-yl)acetamide Chemical class C1=CC=C2NC(NC(=O)C)=NC2=N1 ZWFMOGMVCCFQRG-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- QAXZWHGWYSJAEI-UHFFFAOYSA-N n,n-dimethylformamide;ethanol Chemical compound CCO.CN(C)C=O QAXZWHGWYSJAEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 5
- 239000005695 Ammonium acetate Substances 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 229940043376 ammonium acetate Drugs 0.000 claims description 5
- 235000019257 ammonium acetate Nutrition 0.000 claims description 5
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 239000011345 viscous material Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 230000021736 acetylation Effects 0.000 abstract description 2
- 238000006640 acetylation reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 8
- 238000011160 research Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 239000000976 ink Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000008204 material by function Substances 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000004252 FT/ICR mass spectrometry Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940049706 benzodiazepine Drugs 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- SVUOLADPCWQTTE-UHFFFAOYSA-N 1h-1,2-benzodiazepine Chemical compound N1N=CC=CC2=CC=CC=C12 SVUOLADPCWQTTE-UHFFFAOYSA-N 0.000 description 1
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 description 1
- PRYNJOJHKYNLIS-UHFFFAOYSA-N 6-hydroxynaphthalene-2-carbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(O)=CC=C21 PRYNJOJHKYNLIS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NGWGECKIKGHTIC-UHFFFAOYSA-N [Br].[S].[N] Chemical compound [Br].[S].[N] NGWGECKIKGHTIC-UHFFFAOYSA-N 0.000 description 1
- ABXSJIXCMARDGV-UHFFFAOYSA-N [N].[Br] Chemical compound [N].[Br] ABXSJIXCMARDGV-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005100 correlation spectroscopy Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003193 general anesthetic agent Substances 0.000 description 1
- 238000001052 heteronuclear multiple bond coherence spectrum Methods 0.000 description 1
- 238000000990 heteronuclear single quantum coherence spectrum Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004857 imidazopyridinyl group Chemical group N1C(=NC2=C1C=CC=N2)* 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000932 sedative agent Substances 0.000 description 1
- 230000001624 sedative effect Effects 0.000 description 1
- 230000004799 sedative–hypnotic effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
-
- 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
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- 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
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/30—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing heterocyclic ring with at least one nitrogen atom as ring member
-
- 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
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/10—Organic materials containing nitrogen
-
- 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"
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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
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
Abstract
The invention discloses an acetamido imidazopyridine compound shown in formula I, a preparation method and application thereof, wherein the acetamido imidazopyridine compound is synthesized by one-pot synthesis strategy of three-component and multi-site selective cyclization, and can be used as sky blue fluorescent material in the technical fields of luminescent devices, anti-counterfeiting technology, laser dye, fluorescent probes, fluorescent imaging, light conversion material, fluorescent film, fluorescent ink and the like, the reaction steps are few, the production period is short, the efficiency is high, the process is simple, the operation is convenient, the control is easy, and nitrogen protection and other special equipment are not neededThe amino active site does not need to be sealed in advance, so that the use of toxic and harmful acetylation reagent is avoided, the safety and environmental protection are realized, the production cost is low, and the method is suitable for industrial production:
wherein Ar is selected from any one of the following groups:
Description
technical field:
the invention relates to the technical field of organic functional materials, in particular to an acetamido imidazo pyridine compound, a preparation method and application thereof.
The background technology is as follows:
the organic luminescent material is widely applied to the technical fields of organic electroluminescent devices, organic solid lasers, organic photovoltaic cells, biomedical fluorescent imaging, organic fluorescent sensors, anti-counterfeiting materials, fluorescent probes, fluorescent films, fluorescent toners, fluorescent inks and the like. Along with the rapid development of modern technology, the application field of new chemical materials is continuously expanded, and the design and development of multifunctional organic luminescent materials with strong fluorescence emission, high fluorescence efficiency and adjustable emission wavelength have become research hot spots in the current photoelectric materials and technical fields.
2- (2-amino-5-bromo-benzoyl) pyridine is an important intermediate or metabolite for synthesizing sedative hypnotic anxiolytic drug bromozepam and ultrashort-acting sedative/anesthetic drug r Malun, benzenesulfonic acid r Malun. In the prior art, the research of the preparation method is mostly limited to the research of synthesis methods and process development and analysis and test technology, and the application of the preparation method serving as a medical intermediate in the synthesis of benzodiazepine drugs (BZDs) is directly used as a raw material, and the research of the preparation method for designing and developing the multifunctional organic luminescent material has not been reported yet.
The invention comprises the following steps:
the invention aims to provide an acetamido imidazo pyridine compound, a preparation method and application thereof.
The invention is realized by the following technical scheme:
acetamido imidazopyridines of formula i:
wherein Ar is selected from any one of the following groups:
another object of the present invention is to provide a method for preparing the above acetamido imidazopyridines, which is characterized by the following synthetic route:
wherein Ar is selected from any one of the following groups:
the method comprises the following steps: dissolving 2- (2-amino-5-bromo-benzoyl) pyridine shown in a formula II, substituted aromatic aldehyde shown in a formula III and ammonium acetate in glacial acetic acid in a molar ratio of 1:1-2:8-17, carrying out reflux reaction for 8-10 hours under rapid stirring, cooling the reaction solution to room temperature after the reaction is finished, pouring the reaction solution into ice water under stirring, adjusting pH=7 with an alkali solution, and cooling the mixed solution to room temperature again; if the obtained product is a solid substance, performing reduced pressure suction filtration, washing with water, drying at room temperature, recrystallizing the crude product by using an ethanol-acetone or ethanol-N, N-dimethylformamide mixed solvent, and performing vacuum drying to obtain a target product; if the solid substance is a viscous substance, extracting with dichloromethane, combining the extracts, removing the dichloromethane by rotary evaporation to obtain a solid substance, recrystallizing with ethanol-acetone or ethanol-N, N-dimethylformamide mixed solvent, and drying in vacuum to obtain the target product.
Preferably, the substituted aromatic aldehyde (III) is selected from any one of the following compounds:
further, the alkali solution is ammonia water, or 10-40% sodium hydroxide aqueous solution by mass fraction, or 10-40% potassium hydroxide aqueous solution by mass fraction.
Still another object of the present invention is to protect the use of said acetamido imidazopyridines.
The acetamido imidazopyridine compound can be used as a sky blue fluorescent material in the technical fields of luminescent devices, anti-counterfeiting technologies, laser dyes, fluorescent probes, fluorescent imaging, light conversion materials, fluorescent films, fluorescent ink and the like.
The acetamido imidazo pyridine compound has a good flame retardant function, and can be used as a flame retardant in the related technical field. In addition, the compounds can be used as pharmaceutical intermediates for synthesizing and developing medicaments.
The compound Ia also contains a thioether bond with an antioxidant function, and therefore, the compound also has an antioxidant effect.
The compound Ib has sensitive characteristic to alkaline substances, and the addition of alkali does not quench fluorescence, so that the compound Ib has potential application value in the fields of fluorescent probes, pH detection and the like.
The invention has the following beneficial effects:
(1) The invention has ingenious conception, simultaneously utilizes three reaction sites of 2- (2-amino-5-bromo-benzoyl) pyridine, adopts a three-component and multi-site selective cyclization one-pot synthesis strategy to synthesize the acetamidoimidazopyridine compound in one step, has the advantages of few reaction steps, short production period, high efficiency, simple process, convenient operation, easy control, no need of nitrogen protection and other special equipment, no need of sealing the amino active site in advance, avoids the use of toxic and harmful acetylation reagent, eliminates potential safety hazard, reduces environmental risk, recycles used solvents, is safe and environment-friendly, has low production cost, is suitable for industrial production, realizes the selective construction of an imidazopyridine structure skeleton in multi-active site molecules, can be used for designing and synthesizing functional nitrogen heterocyclic organic functional materials and medicaments, expands the research and application fields of 2- (2-amino-5-bromo-benzoyl) pyridine, has important theoretical value and good application prospect in the fields of organic functional materials and medicaments, and solves the problems of poor reaction selectivity of multi-active site molecules, and low preparation efficiency of target molecules in the prior art.
(2) The acetamido imidazo pyridine compound provided by the invention has good fluorescence emission and stimulus response characteristics, and can emit bright sky blue fluorescence, so that the acetamido imidazo pyridine compound can be used as a sky blue fluorescent material in the technical fields of light emitting devices, anti-counterfeiting technologies, laser dyes, fluorescent probes, fluorescent imaging, light conversion materials, fluorescent films, fluorescent ink and the like.
(3) The acetamido imidazo pyridine compound provided by the invention has a stable molecular structure, a molecular skeleton contains nitrogen and bromine flame-retardant elements, and the compound Ia also contains sulfur flame-retardant elements, so that the compound has a good flame-retardant function, can exert bromine-nitrogen synergistic effect or bromine-nitrogen-sulfur ternary synergistic effect by different flame-retardant mechanisms, has high synergistic flame-retardant efficiency, and is expected to overcome the defect of single flame-retardant element. In addition, the compound Ia also contains a thioether bond having an antioxidant function, and thus, the compound also has an antioxidant effect. The compound Ib has sensitive characteristic to alkaline substances, and the addition of alkali does not quench fluorescence, so that the compound Ib has potential application value in the fields of fluorescent probes, pH detection and the like.
(4) The selected production raw materials are intermediates of related industries such as medicines, are rich in sources, and can provide a new effective way for comprehensive development, utilization and industrial upgrading of related industries.
Description of the drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of compound Ia;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of compound Ia;
FIG. 3 is a nuclear magnetic resonance of Compound Ia 1 H- 1 H COSY profile;
FIG. 4 is a nuclear magnetic resonance of Compound Ia 1 H- 13 C HSQC spectrum;
FIG. 5 is a nuclear magnetic resonance of Compound Ia 1 H- 13 C HMBC spectra;
FIG. 6 is a photograph of the fluorescent color of compounds Ia, ib, ic in dimethylsulfoxide solution. In the left graph, dimethyl sulfoxide (DMSO) solutions of compounds Ia, ib, ic from left to right are yellow, brown, respectively, under white light; in the right panel, dimethylsulfoxide (DMSO) solutions of compounds Ia, ib, ic from left to right emit strong sky blue fluorescence under 365nm uv lamp irradiation.
FIG. 7 is a graph showing the change in fluorescence color (365 nm ultraviolet lamp irradiation) of Compound Ib after adding an alkaline substance to a dimethylsulfoxide solution. The dimethyl sulfoxide solution of the compound Ib is sky blue fluorescent (left), and after a certain amount of alkaline substances are added, the solution is yellow fluorescent (right).
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
The reagents and materials described in the examples below, unless otherwise indicated, are all commercially available.
Experimental instrument and model: bruker AVANCE-300 and AVANCE-500 nuclear magnetic resonance spectrometer; bruker 7.0T SolariX XR FT-ICR-MS Fourier transform ion cyclotron resonance mass spectrometer.
Example 1: preparation of Compound Ia:
2- (2-amino-5-bromo-benzoyl) pyridine (1 mmol) and 2-trifluoromethyl-4-methylthiobenzaldehyde (1 mmol) and ammonium acetate (8 mmol) were dissolved in 50 ml glacial acetic acid in a 100 ml dry round bottom flask and reacted under reflux with rapid stirring for 8 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, poured into ice water with stirring, ph=7 was adjusted with ammonia water, the reaction mixture was cooled again to room temperature, the obtained viscous substance was extracted 3 times with dichloromethane, the extracts were combined, dichloromethane was removed by rotary evaporation, and a yellow solid substance was obtained, which was dried at room temperature. The crude product is recrystallized by ethanol-acetone mixed solvent and dried in vacuum to obtain yellow solid, namely the compound Ia with the yield of 53%.
1 H NMR(300MHz,DMSO-d 6 /TMS)δ:1.98(s,3H),2.65(s,3H),6.85(t,J＝6.3Hz,1H),7.10(dd,J＝9.0,6.3Hz,1H),7.49(dd,J＝8.7,2.4Hz,1H),7.76-7.85(m,5H),7.93(d,J＝6.9Hz,1H),8.29(d,J＝8.7Hz,1H),10.91(s,1H)； 13 C NMR(125MHz,DMSO-d 6 /TMS)δ:14.61,24.78,114.85,115.78,118.22,122.83,123.17,123.26,123.78,123.83,124.98,125.18,127.03,128.42,129.74,129.95,130.19,130.39,133.67,133.76,135.40,143.38,168.47。
Meanwhile, the molecular structure of the compound Ia is further confirmed by a two-dimensional nuclear magnetic resonance spectrometer by using a 500MHz nuclear magnetic resonance spectrometer, and the details are shown in figures 3-5.
Example 2: preparation of Compound Ib:
2- (2-amino-5-bromo-benzoyl) pyridine (1 mmol) and 2-hydroxy-1-naphthaldehyde (2 mmol) and ammonium acetate (17 mmol) were dissolved in 50 ml glacial acetic acid in a 100 ml dry round bottom flask and reacted under reflux with rapid stirring for 10 hours; after the reaction was completed, the reaction solution was cooled to room temperature, poured into ice water with stirring, ph=7 was adjusted with aqueous sodium hydroxide solution, the obtained solid was suction-filtered under reduced pressure, washed with water 3 times, and the crude product was recrystallized from ethanol-N, N-dimethylformamide mixed solvent, and dried in vacuo to give a yellow solid with a yield of 58%.
1 H NMR(300MHz,DMSO-d 6 /TMS)δ:2.00(s,3H),6.82(t,J＝6.9Hz,1H),7.11(dd,J＝9.0,6.3Hz,1H),7.36-7.54(m,5H),7.69(d,J＝7.2Hz,1H),7.87-7.95(m,3H),8.04(d,J＝9.0Hz,1H),8.32(d,J＝9.0Hz,1H),10.44(s,1H)，11.31(s,1H)。HRMS m/z:472.06552([M+H] + ,
C 25 H 19 BrN 3 O 2 )。
Example 3: preparation of Compound Ic:
2- (2-amino-5-bromo-benzoyl) pyridine (1 mmol) and 6-hydroxy-2-naphthaldehyde (1.5 mmol) and ammonium acetate (12 mmol) were dissolved in 50 ml glacial acetic acid in a 100 ml dry round bottom flask and reacted under reflux with rapid stirring for 9 hours; after the reaction was completed, the reaction mixture was cooled to room temperature, poured into ice water under stirring, ph=7 was adjusted with an aqueous potassium hydroxide solution, and the obtained solid was suction-filtered under reduced pressure, washed 3 times with water, and dried at room temperature. The crude product was recrystallized from ethanol-N, N-dimethylformamide mixed solvent and dried in vacuo to give a dark green solid with a yield of 51%.
1 H NMR(300MHz,DMSO-d 6 /TMS)δ:2.09(s,3H),6.92(t,J＝6.9Hz,1H),7.05-7.23(m,3H),7.49(dd,J＝9.0,2.4Hz,1H),7.75-7.96(m,5H),8.24(d,J＝8.7Hz,1H),8.36(s,1H)，8.68(d,J＝7.2Hz,1H),10.00(s,1H)，11.13(s,1H)； 13 C NMR(75MHz,DMSO-d 6 /TMS)δ:24.54,108.70,119.42,121.93,123.19,125.80,126.66,126.92,127.38,128.58,129.58,130.12,134.56,135.00,137.38,156,36,168.06.
Example 4: preliminary test of fluorescence Property
The results show that:
1. the compound Ia solid shows yellow green fluorescence under 365nm ultraviolet lamp irradiation, and the compound Ib and Ic solid has weak or no fluorescence under 365nm ultraviolet lamp irradiation.
2. The Dimethylsulfoxide (DMSO) solutions of compounds Ia, ib and Ic were yellow, brown, respectively, under white light and the solutions all emitted strong sky blue fluorescence under 365nm uv lamp irradiation, see fig. 6.
3. Further research shows that the compound Ib molecule has better stimulus response characteristic to alkaline substances. After a certain amount of alkaline substances (0.1M sodium hydroxide solution) is added into the dimethyl sulfoxide solution of the Ib molecule of the compound, the color of the solution is not obviously changed and is still yellow, but the sky blue fluorescence is converted into yellow fluorescence under the irradiation of a 365nm ultraviolet lamp; after a certain amount of acidic substance (acetic acid) was further added to the system, the fluorescence color of the solution was observed to be recovered from yellow to sky blue under irradiation of 365nm ultraviolet lamp, see fig. 7. The compound Ib has sensitive property to alkaline substances, and the addition of alkali does not quench fluorescence, so that the compound Ib has potential application value in the fields of fluorescent probes, pH detection and the like.
Therefore, the novel functional nitrogen heterocyclic compound provided by the invention can be used as a sky blue fluorescent material in the technical fields of light emitting devices, anti-counterfeiting technologies, laser dyes, fluorescent probes, fluorescent imaging, light conversion materials, fluorescent films, fluorescent ink and the like.
Claims (8)
1. Acetamido imidazopyridines of formula i:
wherein Ar is selected from any one of the following groups:
2. the process for the preparation of acetamido imidazopyridines according to claim 1, characterized in that the synthetic route is as follows:
wherein Ar is selected from any one of the following groups:
the method comprises the following steps: dissolving 2- (2-amino-5-bromo-benzoyl) pyridine, substituted aromatic aldehyde shown in a formula III and ammonium acetate in glacial acetic acid in a molar ratio of 1:1-2:8-17, carrying out reflux reaction for 8-10 hours under rapid stirring, cooling the reaction solution to room temperature after the reaction is finished, pouring the reaction solution into ice water under stirring, regulating pH=7 with alkali solution, and cooling the mixed solution to room temperature again; if the obtained product is a solid substance, performing reduced pressure suction filtration, washing with water, drying at room temperature, recrystallizing the crude product by using an ethanol-acetone or ethanol-N, N-dimethylformamide mixed solvent, and performing vacuum drying to obtain a target product; if the solid substance is a viscous substance, extracting with dichloromethane, mixing the extracts, removing the dichloromethane by rotary evaporation to obtain a solid substance, recrystallizing with ethanol-acetone or ethanol-N, N-dimethylformamide mixed solvent, and drying in vacuum to obtain the target product.
3. The preparation method according to claim 2, wherein the alkaline solution is aqueous ammonia or 10-40% aqueous sodium hydroxide solution or 10-40% aqueous potassium hydroxide solution.
4. Use of acetamido imidazopyridines according to claim 1.
5. The use according to claim 4, wherein acetamidoimidazopyridines are used as sky blue fluorescent materials in the fields of light emitting devices, security technologies, laser dyes, fluorescent probes, fluorescent imaging, light conversion materials, fluorescent films, fluorescent ink technologies.
6. The use according to claim 4, wherein said acetamidoimidazopyridines are flame retardants.
7. The use according to claim 4, wherein the compound Ib is used in the field of fluorescent probes, pH detection.
8. The use according to claim 4, wherein compound Ia is used as an antioxidant.
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