CN111303016A - Synthesis of 4' -substituted bipyridine compound - Google Patents

Synthesis of 4' -substituted bipyridine compound Download PDF

Info

Publication number
CN111303016A
CN111303016A CN201811513001.0A CN201811513001A CN111303016A CN 111303016 A CN111303016 A CN 111303016A CN 201811513001 A CN201811513001 A CN 201811513001A CN 111303016 A CN111303016 A CN 111303016A
Authority
CN
China
Prior art keywords
tpy
compound
bipyridine
phenyl
synthesis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811513001.0A
Other languages
Chinese (zh)
Inventor
陈萌
朱超云
宋伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Polytechnic Institute
Original Assignee
Nanjing Polytechnic Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Polytechnic Institute filed Critical Nanjing Polytechnic Institute
Priority to CN201811513001.0A priority Critical patent/CN111303016A/en
Publication of CN111303016A publication Critical patent/CN111303016A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • 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
    • 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
    • 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
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-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
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Immunology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Molecular Biology (AREA)
  • Pyridine Compounds (AREA)

Abstract

The invention designs and synthesizes a compound which uses flexible open-chain crown ether as a connecting group to bridge a double-fluorescent group 4 '-phenyl-2, 2':6', 2' -terpyridine by using p-methylbenzenesulfonyl chloride, triethylene glycol, 4-methoxybenzaldehyde, 2-acetylpyridine and the like as raw materials: 4,4' -Ethylenedioxy-bridged bis-4 ' -phenyl-2, 2':6', 2' -bipyridine (TPY-1). Use of the synthesized compound TPY-11HNMR、13The CNMR and the MS are characterized, have correct structures, and research the properties of UV-Vis absorption spectrum and fluorescence emission spectrum of TPY-1 and metal complexes thereof. Compound TPY-1 at neutral and low concentration of HClO4In solution, it shows p-Mg2+High sensitivity and selectivity.

Description

Synthesis of 4' -substituted bipyridine compound
Technical Field
The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a method for synthesizing a compound which uses flexible open-chain crown ether as a connecting group to bridge a double-fluorescent group 4 '-phenyl-2, 2':6', 2' -terpyridine: 4,4' -ethylenedioxy-diethoxy-bridged bis-4 ' -phenyl-2, 2':6', 2' -bipyridine.
Background
2,2', 6', 2' -bipyridine (TPY) is a typical oligomeric pyridine ligand, which can be coordinated with a plurality of metal ions to form various complexes with transition metals and lanthanide metals, the photophysical and photochemical properties of the complexes are widely and deeply researched, the complexes can be applied to solar energy conversion, fluorescence labeling and the like, and the TPY ligand can also be used for constructing supermolecular structure and functional nano materials. The 4' -substituted bipyridine and its derivative are ligands with excellent properties, play an important role in the field of coordination chemistry, can react with most metals such as transition metals, alkali metals, multicolored metals and the like, have important value in the aspects of fluorescent devices and materials, self-assembled construction patterns and the like, can also be used for luminescence analysis of metal complexes, and provide a powerful tool for analytical chemists. By functionalizing the 4' position of the terpyridine, not only can the strong tridentate chelating coordination of the terpyridine be utilized, but also coordination points can be increased; different substituents will cause differences in coordination capacity and complex structure, and can also adjust and improve various properties of the material to different degrees. Crown ethers, a macrocyclic molecule, possess a unique cyclic structure, and due to their unique chemical modification and coordination abilities, are widely used in supramolecular chemistry to construct structural modules or molecular frameworks by coordinating with metal ions. The open-chain crown ether is in a linear structure, can be converted into a ring structure after being bonded with metal ions, and can be designed into a cationic fluorescent probe with better sensitivity if the structure is changed along with the change of physical signals, such as the change of ultraviolet absorption, fluorescence and the like.
Disclosure of Invention
The invention provides a synthetic scheme, and synthesizes a compound which uses flexible open-chain crown ether as a connecting group to bridge a double-fluorescent group 4 '-phenyl-2, 2':6', 2' -bipyridine.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a compound which uses flexible open-chain crown ether as a connecting group to bridge a double-fluorescent group 4 '-phenyl-2, 2' -6 ', 2' -bipyridine is designed and synthesized by using p-methylbenzenesulfonyl chloride, triethylene glycol, 4-methoxybenzaldehyde, 2-acetylpyridine and the like as raw materials: 4,4' -Ethylenedioxy-bridged bis-4 ' -phenyl-2, 2':6', 2' -bipyridine (TPY-1). Use of the synthesized compound TPY-11HNMR、13The CNMR and the MS are characterized, have correct structures, and research the properties of UV-Vis absorption spectrum and fluorescence emission spectrum of TPY-1 and metal complexes thereof. Compound TPY-1 at neutral and low concentration of HClO4In solution, it shows p-Mg2+High sensitivity and selectivity.
The compound is synthesized from the following raw materials: 2-acetylpyridine, 4-methoxybenzaldehyde and triethylene glycol.
The synthetic route of the compound is shown in figure 1.
The synthesis method of the compound comprises the following steps:
(1) synthesis of 4' - (4-methoxyphenyl) -2,2':6',2 "-bipyridine: in a 250 mL flask, 2.72 g (20.0 mmol) of 4-methoxybenzaldehyde, 4.84 g (40.0 mmol) of 2-acetylpyridine and 100 mL of ethanol were added, and after thorough mixing, 3.08 g of solid KOH (85%) and 60 mL of aqueous ammonia (29.3%) were added, followed by stirring at 40 ℃ for 5 hours. The solution was cooled to room temperature, a dark green solid precipitated, filtered, washed with 10 mL cold ethanol and the crude product was EtOH/CHCl3(1:1, v/v) recrystallization gave 3.32 g of colorless crystals.
(2) Synthesis of 4' - (4-hydroxyphenyl) -2,2':6',2 "-bipyridine (TPY-3): in a 250 mL flask, 0.5 g of the above synthesized 4' - (4-methoxyphenyl) -2,2':6',2 "-bipyridine, 10 mL of acetonitrile, 10 mL of aqueous HBr (48%) were added, shaken well, dissolved, the solution was cooled to room temperature under 90 ℃ (refluxing and stirring 6 h), and then NaOH solution was added dropwise to adjust p H to 10-11, followed by extraction with CH2Cl 2. after the extract was spin-dried, 10 mL of butanol was added to the product, after dissolution, p H was adjusted to 5-6 with HCl, after spin-drying, the crude product was recrystallized from a mixture of butanol and ethanol (1:1, v/v) to obtain 0.34 g of colorless crystals.
(3) Synthesis of triethylene glycol di-p-toluenesulfonate: in a 250 mL two-necked flask, 4 g of triethylene glycol, 50 mL of tetrahydrofuran, 3.5 g of NaOH (ground powder), and 50 mL of water were sequentially added, stirred for 5 hours, and 10g of a THF solution of p-toluenesulfonyl chloride was added dropwise thereto and reacted at room temperature for 2 hours. After the reaction is finished, standing for a period of time, separating an organic layer, removing tetrahydrofuran by rotary evaporation to obtain a viscous liquid, and separating by column chromatography (1:1 of ethanolamine PE and ethyl acrylate EA as eluent) to obtain 9.2 g of colorless viscous liquid.
(4) Synthesis of TPY-1: in a 250 mL flask, 0.15 g K was added sequentially2CO3（1.0 mmol）、10 mL acetonitrile, 0.325 g of 4'- (4-hydroxyphenyl) -2,2':6', 2' -bipyridine (1.0 mmol). After shaking, a mixture of 0.22 g of triethylene glycol bis-p-toluenesulfonate (0.48 mmol) and 10 mL of acetonitrile was slowly added dropwise thereto under nitrogen charging (about 2 h) while stirring, followed by heating to 60 ℃ and refluxing for 24 h. After the reaction was completed, acetonitrile was removed by rotary evaporation under reduced pressure to obtain a dark brown viscous solid, which was washed with distilled water, chloroform, and ethanol, followed by filtration and drying in vacuo to obtain pure light brown powder (TPY-1) 0.516 g.
The compound provided by the invention is suitable for identifying metal magnesium ions in HClO4The concentration is 1X 10-4At mol/L, the reaction is carried out to 1X 10-5Adding 1X 10 drops of acetonitrile solution of mol/L TPY-1-4mol/L Li+、Na+、K+、Ba2+、Cu2+、Mg2 +、Ca2+、Zn2+、Cd2+、Mn2+、Cr3+、Ni2+、Co2+、Pb2+、Fe2+、Hg2+. At 1X 10-5Adding 1X 10 to the acetonitrile solution of mol/L TPY-1-4HClO in mol/L concentration4After that, the fluorescence of TPY-1 was completely quenched. Then Li is added to the solution separately+、Na+、K+、Ba2+、 Cu2+、Ca2+、Zn2+、Cd2+、Mn2+、Cr3+、Ni2+、Co2+、Pb2+、Fe2+、Hg2+TPY-1 shows little change in fluorescence, only Mg is added2+Then, the fluorescence of TPY-1 is obviously enhanced, and the fluorescence intensity is more than 10 times of that of other metal ions.
The invention has the beneficial effects that: the invention synthesizes a novel open-chain crown ether bridged bis 4 '-phenyl-2, 2', 6', 2' -terpyridine (TPY-1) at low concentration (C)HClO4/ CMg2+＜ 100） HClO4In solution, TPY-1 is suitable for detecting Mg2+And the method shows better selectivity and higher sensitivity.
Drawings
Figure 1 is a scheme of the synthesized compounds.
FIG. 2 is a drawing of compound TPY-11H NMR。
FIG. 3 is a 13C NMR spectrum of compound TPY-1.
FIG. 4 is a mass spectrum of compound TPY-1.
Detailed Description
For better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Example 1: characterization of the synthetic Structure of the Compounds
Subject the synthesized target compound to1H NMR、13C NMR and MS analyses showed that the spectra are shown in FIG. 2, FIG. 3 and FIG. 4, respectively. From the analysis results of the data, it was found that TPY-1 had a correct structure.
1H NMR (300 MHz, CDCl3) δ (ppm): 8.67 (m, 12H, 3,6, 3′,5′, 3″,6″-H),7.82 (d,J= 7.9 Hz, 8H, 4,4″-H and phenyl 2,6-H), 7.32 (m, 4H, 5,5″-H), 7.04(d,J= 8.61 Hz, 4H, phenyl 3,5-H), 4.02 (s, 4H, OCH2), 3.91 (m, 4H, CH2O),3.79 (s, 4H, OCH2) .13C NMR (300 MHz, CDCl3) δ (ppm): 159.74, 156.19, 155.60,149.69, 148.92, 136.91, 130.78, 128.47, 123.71, 121.37, 118.31, 114.99,114.32. TOF-MS：m/z calcd for (M+H+)C54H40N6O4765.32; found 765.40.

Claims (3)

1. The synthesis of the 4' -substituted bipyridine compound is characterized in that: compounds in which the double fluorophore 4' -phenyl-2, 2':6',2 "-bipyridine is bridged with a flexible open-chain crown ether as the linking group: 4,4' -ethylenedioxy-diethoxy-bridged bis-4 ' -phenyl-2, 2':6', 2' -bipyridine.
2. The compound of claim 1, synthesized from the following starting materials: p-methylbenzenesulfonyl chloride, triethylene glycol, 4-methoxybenzaldehyde, 2-acetylpyridine and the like are used as raw materials.
3. The compound of claim 1 that is selective for magnesium ions, wherein: TPY-1 in low-concentration (C HClO4/CMg2+ < 100) HClO4 solution is suitable for detecting Mg2+, and shows better selectivity and higher sensitivity.
CN201811513001.0A 2018-12-11 2018-12-11 Synthesis of 4' -substituted bipyridine compound Pending CN111303016A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811513001.0A CN111303016A (en) 2018-12-11 2018-12-11 Synthesis of 4' -substituted bipyridine compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811513001.0A CN111303016A (en) 2018-12-11 2018-12-11 Synthesis of 4' -substituted bipyridine compound

Publications (1)

Publication Number Publication Date
CN111303016A true CN111303016A (en) 2020-06-19

Family

ID=71157825

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811513001.0A Pending CN111303016A (en) 2018-12-11 2018-12-11 Synthesis of 4' -substituted bipyridine compound

Country Status (1)

Country Link
CN (1) CN111303016A (en)

Similar Documents

Publication Publication Date Title
CN111875642B (en) Poly-terpyridyl metal organic ligand compound, five-membered flower ring-shaped supramolecule assembled by same and preparation method of five-membered flower ring-shaped supramolecule
Yang et al. Facile synthesis of zinc halide-based ionic liquid for efficient conversion of carbon dioxide to cyclic carbonates
CN101631775A (en) Metal complex
Han et al. Aggregation-induced emission behavior of a pH-controlled molecular shuttle based on a tetraphenylethene moiety
CN112062756A (en) Mannhouse donor-acceptor adduct of furan and 3-pyridine ethylamine activated by Merlox acid and synthetic method thereof
Klein et al. Convenient synthesis of tridentate 2, 6-di (pyrazol-1-yl)-4-carboxypyridine and tetradentate 6, 6′-di (pyrazol-1-yl)-4, 4′-dicarboxy-2, 2′-bipyridine ligands
CN111039970B (en) Pyridyl boron dipyrromethene derivative dye ligand and preparation method thereof
CN105949168B (en) A kind of method for synthesizing heterochromatic ketone compounds
CN115028849A (en) Preparation method and application of metal triangular supramolecules with room-temperature fluorescence
CN110449183A (en) Ionic iron (III) complex is preparing the application in allylic amines compound
CN111303016A (en) Synthesis of 4&#39; -substituted bipyridine compound
CN115181282B (en) Double-layer eight-element hollow annular metal organic supermolecule and synthesis method thereof
CN115093572B (en) Polypyridine ring metal iridium supermolecular material, preparation method and application
CN107652206B (en) Acenaphthylene skeleton large steric hindrance alpha-diimine compound and synthesis method thereof
CN111349121A (en) Cobalt carbonyl complex and preparation method thereof
CN103539790A (en) Rotaxane molecular machine of naphthalimide crown ether and pH meter based on rotaxane molecular machine
CN105209435A (en) Pyridine- or pyrazine-containing compounds
CN110386903B (en) Tetrazine-containing oligomeric phenylene acetylene compound and preparation method thereof
CN108329325B (en) Synthesis method of 8-azachromone
CN106565604B (en) A kind of synthetic method of 5- nitro -8- amide groups quinolines
CN115785466B (en) Preparation method and application of supermolecular material with green photooxidation effect
CN105384744B (en) Four (trifluoro ethoxy) phthalocyanine europium complexes and its preparation method and application
US9902743B2 (en) Copper complex for capturing carbon dioxide
Ou et al. Synthesis and characterization of macrocyclic compounds with a hydroxyl functional group
Hu et al. Construction of a hetero pseudo [2] rota [2] catenane

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200619

WD01 Invention patent application deemed withdrawn after publication