CN107857773A - 2-azaaromatic ring substituted quinazolinone borides - Google Patents
2-azaaromatic ring substituted quinazolinone borides Download PDFInfo
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- CN107857773A CN107857773A CN201710088903.3A CN201710088903A CN107857773A CN 107857773 A CN107857773 A CN 107857773A CN 201710088903 A CN201710088903 A CN 201710088903A CN 107857773 A CN107857773 A CN 107857773A
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- quinazolinone
- phenyl
- boride
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- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical class C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- -1 substituted-phenyl Chemical group 0.000 claims description 54
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000012074 organic phase Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 22
- 238000004440 column chromatography Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000006467 substitution reaction Methods 0.000 claims description 15
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 claims description 6
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 claims description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 5
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 3
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 3
- 150000002460 imidazoles Chemical class 0.000 claims description 3
- 150000002475 indoles Chemical class 0.000 claims description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003233 pyrroles Chemical class 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 229960001860 salicylate Drugs 0.000 claims description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims description 2
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 claims description 2
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003851 azoles Chemical class 0.000 claims 2
- 125000005605 benzo group Chemical group 0.000 claims 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims 2
- INKDAKMSOSCDGL-UHFFFAOYSA-N [O].OC1=CC=CC=C1 Chemical class [O].OC1=CC=CC=C1 INKDAKMSOSCDGL-UHFFFAOYSA-N 0.000 claims 1
- 239000012153 distilled water Substances 0.000 claims 1
- 125000000623 heterocyclic group Chemical group 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical class [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052796 boron Chemical class 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical group CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 239000000049 pigment Substances 0.000 abstract 1
- 125000006617 triphenylamine group Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 36
- 238000006862 quantum yield reaction Methods 0.000 description 32
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 27
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 16
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 238000004949 mass spectrometry Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 238000004821 distillation Methods 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- QMNUDYFKZYBWQX-UHFFFAOYSA-N 1H-quinazolin-4-one Chemical compound C1=CC=C2C(=O)N=CNC2=C1 QMNUDYFKZYBWQX-UHFFFAOYSA-N 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 229910015900 BF3 Inorganic materials 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000000284 extract Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002027 dichloromethane extract Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 0 C*(CC=C)(*12)*3c(C=C)c(C=C)ccc3C1=*c1ccccc1C2O Chemical compound C*(CC=C)(*12)*3c(C=C)c(C=C)ccc3C1=*c1ccccc1C2O 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000003384 imaging method Methods 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- 238000002428 photodynamic therapy Methods 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- 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
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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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- 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
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
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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
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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
- C09K2211/1055—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms with other heteroatoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Electroluminescent Light Sources (AREA)
- Plural Heterocyclic Compounds (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The invention relates to a novel high-efficiency organic fluorescent molecule-2-nitrogen heterocyclic aromatic ring substituted quinazolinone boride, wherein the 2-nitrogen heterocyclic aromatic ring substituted quinazolinone boride can be synthesized by taking 2-nitrogen heterocyclic aromatic ring substituted quinazolinone compounds and boron-containing compounds as raw materials. Because other groups can be introduced into the 2-nitrogen heteroaromatic ring substituted quinazolinone parent body, a novel functional pigment material can be synthesized by reacting with different borides, for example, a conjugated aromatic ring or an aromatic heterocyclic ring is introduced, so that a conjugated system can be enlarged, or electron-donating groups such as triphenylamine, diethylamine and the like are introduced, so that the emission wavelength of the compounds moves towards the long-wave direction, and novel fluorescent molecules with various emission wavelengths are obtained. The fluorescent material prepared by the molecule can be widely applied to the fields of luminescent and display devices, chemical industry, biological medicine, pesticides, military industry, intelligent terminals and the like.
Description
Technical field
The present invention relates to Functional dye field, and in particular to a kind of new luminescent organic molecule --- 2- nitrogen heteroaromatic rings take
The quinazolinone boride in generation.
Background technology
The multiple color and excellent luminescent properties that feature organic pigment molecule can be presented with it, and unique processing
Performance, can convenient regulation molecular structure, favored for a long time by researcher, and light emitting diode, solar cell, field effect
Answer transistor, multifunctional intellectual display terminal, biomedical imaging, photodynamic therapy, communication and signal transduction, environment inspection
The fields such as survey, sensor are widely used, and are one of study hotspots of functional form organic molecule in recent years.
Boron has unique steric configuration and electronic structure, former by introducing boron in functional form organic pigment molecular structure
Son, its Photophysics can be effectively adjusted, while boracic organic compound also has special chemical stability.Particularly four
The organic B complexs of corrdination type, luminescent properties are superior, because its high molar absorption coefficient, good photostability and chemistry are steady
It is qualitative, got in terms of Organic Light Emitting Diode OLED, and metal ion sensing, cell imaging, photodynamic therapy
Carry out more applications.But synthesis step is more, purifying is complex, particularly classical BODIPY type boracics complex dye point
Son.
By two nitrogen ligands of Quinazolinone-containing construction unit, (or it is corresponding derivative by simple synthesis step by the present invention
Thing) it is coordinated with boron, the quinazolinone boride of a kind of new 2- nitrogen heteroaromatic rings substitution is obtained, is a kind of new organic hair
Luminescent material.In this way, it can further expand effective conjugated system in quinazolinone molecular structure, realize and improve material
Luminous efficiency itself, launch wavelength is adjusted, or even change illumination mode, extend the purpose of luminescent lifetime.Due to the boron after coordination
Complex space structure is X-type, can suppress the accumulation between molecule-molecule, and be expected to obtain has preferably under solution and solid-state
The luminescent material of luminescent properties.There is potential application value in terms of display device, electronic material, biological medicine.
The content of the invention
It is an object of the invention to provide a kind of new luminescent organic molecule --- the quinazolinone of 2- nitrogen heteroaromatic rings substitution
Boride and preparation method thereof.
The quinazolinone boride of a kind of 2- nitrogen heteroaromatic rings substitution, has the general structure such as following formula I or formula II：
Wherein, nitrogen heteroaromatic rings (A rings) can be：Pyrroles, pyridine, quinoline, indoles, thiazole, oxazole, imidazoles, benzothiazole,
Benzoxazoles, benzimidazole, pyridazine, pyrazine, pyrimidine, quinoxaline, purine etc..
Functional group X can be halogen atom, alkynyl, phenyl, substituted-phenyl, hydroxyl, alkyl, alkoxy, phenol epoxide, substitution
The groups such as phenol epoxide, cyano group, adjacent diphenol epoxide, the adjacent diphenol epoxide of substitution, salicylate, substituted salicylic acid root.
R1~R2 can be alkyl, halogen atom, alkenyl, alkynyl, phenyl, substituted-phenyl, aryl, substituted aryl, hydroxyl,
Alkoxy, phenol epoxide, acyl group, aldehyde radical, carboxyl, amide groups, nitro, amino, substituted-amino, heterocyclic radical, substituted heterocyclic radical, cyanogen
The groups such as base, sulfonic group, sulfydryl, alkylthio group.
The quinazolinone boride of above-mentioned 2- nitrogen heteroaromatic rings substitution can by Quinazolinone-containing construction unit two nitrogen ligands (or
Its corresponding derivative) with boron compound be Material synthesis.
The preparation method of the quinazolinone boride of above-mentioned 2- nitrogen heteroaromatic rings substitution：
In the round-bottomed flask of lucifuge, two nitrogen ligands for adding a certain amount of Quinazolinone-containing construction unit (or accordingly spread out
Biology), in non-polar solven, back flow reaction some hours, corresponding boride is added according to specific reaction therebetween.Use high pressure
Liquid chromatogram (HPLC) and thin-layer chromatography (TLC) track whole course of reaction, judge reaction end.After reaction terminating, reaction solution
After the processing such as scrubbed, extraction, obtained extract is concentrated with Rotary Evaporators, removes the mixture obtained after solvent, is utilized
Column chromatography chromatogram separates, and obtains target product.
Obtained target product is dissolved in deuterated reagent DMSO-d6 or CDCl3In, it can pass through1H NMR,13C NMR,
The methods of HRMS, confirms to product structure.
The fluorescence property measure of the quinazolinone boride of this kind of 2- nitrogen heteroaromatic rings substitution, is mainly included the following steps that：
(1) product is dissolved in acetonitrile solvent, is configured to finite concentration, determine compound most using XRF
Big excitation wavelength and maximum emission wavelength, according to maximum excitation wavelength and the maximum emission wavelength numerical measuring product in solution shape
Fluorescence quantum yield under state.
(2) solid powder of compound products is directly placed into XRF, determines compound products solid-state like
Maximum excitation wavelength and maximum emission wavelength under state, according to maximum excitation wavelength and the maximum emission wavelength numerical measuring product
Fluorescence quantum yield under solid states.
The quinazolinone boride of this kind of 2- nitrogen heteroaromatic rings substitution can be used for preparing highly efficient fluorescent material, preparation it is efficient
Fluorescent material has the advantages that property is stable, preserve the convenient, visibility of material and brightness is high.
Beneficial effects of the present invention：The quinazolinone boride and other existing boron of the 2- nitrogen heteroaromatic rings substitution of the present invention
Compound phase ratio has that fluorescence quantum efficiency is high, all possesses the preferable characteristics of luminescence, synthesis under solution and solid-state two states
It is easy, yield is higher, can be the even feather weight large-scale production of gram level the advantages that；Introduced by group, the launch wavelength of compound
It can be moved to long wave direction, and then obtain new, the fluorescence molecule with various launch wavelengths, these molecules can be used for preparing
Highly efficient fluorescent material；The preparation method of the present invention is simple, raw material is easy to get, yield is higher, and therefore, this new compound can answer
For fields such as luminous and display device, chemical industry, biological medicine, agricultural chemicals, military project, intelligent terminals, and it is China in functional material
A kind of novel fluorescent material is developed in field.
Brief description of the drawings
Fig. 1 is the quinazolinone boron compound prepared by example 11H NMR spectras.
Fig. 2 is the quinazolinone boron compound prepared by example 113C NMR spectras.
Fig. 3 is the crystal structure figure of the quinazolinone boron compound prepared by example 1.
Fig. 4 is uv absorption spectra of the quinazolinone boron compound in acetonitrile prepared by example 1.
Fig. 5 is fluorescence emission spectrogram of compound of the quinazolinone boron compound in acetonitrile prepared by example 1.
Fig. 6 is fluorescence emission spectrogram of compound of the quinazolinone boron compound under solid states prepared by example 1.
Fig. 7 is luminous photo of the quinazolinone boron compound under solution and solid states prepared by example 1.
Embodiment
With reference to instantiation, the present invention is further elaborated, but patent right is not limited to these embodiments.
Embodiment 1：
In 100mL reactors, 6- bromo- 2- (2- pyridine radicals) -3- hydrogen quinazoline-4-one 3.50g (10mmol) are added, are added
It is solvent to enter 50mL toluene, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second
Ether compound, backflow is heated to, reacts 24h, reaction material liquid is poured into water by reaction after terminating, and is stood, and layering, uses dichloro
Methane extracts, and organic phase uses NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for the aqueous solution, distillation water washing
The mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 88%.It is product below
Nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR(400MHz,CDCl3) δ=9.14-9.16 (m, 1H), 8.70-8.74 (m, 1H), 8.61-8.63 (m,
1H),8.29-8.30(m,1H),8.20-8.23(m,1H),8.03-8.06(m,1H),7.78-7.80(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=160.8,150.1,148.0,147.3,145.6,142.6,138.0,
130.6,130.3,129.1,125.0,122.5,121.3ppm.
HRMS m/z[M+H]+calcd:349.9906；found:349.9910.
Fluorescence quantum yield：0.94 (solution), 0.30 (solid-state)
Following table is the associated light performance parameter of the product prepared by embodiment 1：
Embodiment 2：
In 100mL reactors, 2- (2- quinolyls) -3- hydrogen quinazoline-4-one 3.21g (10mmol) are added, are added
50mL toluene is solvent, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into BFEE
Compound, backflow is heated to, reacts 24h, reaction material liquid is poured into water by reaction after terminating, and is stood, and layering, uses dichloromethane
Alkane extracts, and organic phase uses NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for the aqueous solution, distillation water washing
The mixture obtained after agent, is separated using column chromatography chromatogram, obtained target product, yield 85%.It is the core of product below
Magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR(400MHz,CDCl3) δ=8.35-8.33 (m, 1H), 8.08-8.06 (m, 1H), 7.88-7.80 (m,
2H),7.60-7.58(m,2H),7.52-7.53(m,1H),7.42-7.45(m,3H)ppm.
13C NMR (100MHz, CDCl3) δ=175.6,163.8,154.3,149.4,147.5,134.9,132.7,
131.6,129.8,129.0,128.0,127.4,126.8,126.3,122.5,121.8,118.6ppm.
HRMS m/z[M+H]+calcd:322.0958；found:322.0963.
Fluorescence quantum yield：0.90 (solution), 0.50 (solid-state)
Embodiment 3：
In 100mL reactors, 6- bromo- 2- (2- pyridine radicals) -3- hydrogen quinazoline-4-one 4.00g (10mmol) are added, are added
It is solvent to enter 50mL toluene, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second
Ether compound, backflow is heated to, reacts 24h, reaction material liquid is poured into water by reaction after terminating, and is stood, and layering, uses dichloro
Methane extracts, and organic phase uses NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for the aqueous solution, distillation water washing
The mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 85%.It is product below
Nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR(400MHz,CDCl3) δ=8.32-8.34 (m, 1H), 8.05-8.07 (m, 1H), 7.84-7.86 (m,
2H),7.61-7.63(m,2H),7.52-7.53(m,1H),7.42-7.45(m,2H)ppm.
13C NMR (100MHz, CDCl3) δ=175.1,163.0,154.0,149.1,147.5,134.5,132.2,
131.0,129.2,128.6,127.8,127.1,126.3,126.0,122.1,121.5,118.0ppm.
HRMS m/z[M+H]+calcd:400.0063；found:400.0058.
Fluorescence quantum yield：0.82 (solution), 0.56 (solid-state)
Embodiment 4：
In 100mL reactors, 6- dimethylaminos -2- (2- pyridine radicals) -3- hydrogen quinazoline-4-ones 3.64g is added
(10mmol), it is solvent to add 50mL toluene, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into three
Boron fluoride ether complex, backflow being heated to, react 24h, reaction material liquid is poured into water by reaction after terminating, and is stood,
Layering, is extracted, organic phase uses NaHCO respectively with dichloromethane3The aqueous solution, distill water washing several times, organic phase rotary evaporation
Instrument concentrates, and removes the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 85%.With
Under be product nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR(400MHz,CDCl3) δ=8.12-8.14 (m, 1H), 8.01-8.03 (m, 1H), 7.74-7.76 (m,
2H),7.51-7.53(m,2H),7.32-7.33(m,1H),7.22-7.25(m,2H),3.35(s,6H)ppm.
13C NMR (100MHz, CDCl3) δ=170.1,160.0,151.0,145.1,142.5,130.5,130.2,
129.8,128.2,127.5,126.4,125.1,124.3,123.0,122.1,121.5,118.0,45.2ppm.
HRMS m/z[M+H]+calcd:365.1380；found:365.1386.
Fluorescence quantum yield：0.89 (solution), 0.41 (solid-state)
Embodiment 5：
In 100mL reactors, 6- phenylacetylene bases -2- (2- pyridine radicals) -3- hydrogen quinazoline-4-ones 4.21g is added
(10mmol), it is solvent to add 50mL toluene, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into three
Boron fluoride ether complex, backflow being heated to, react 24h, reaction material liquid is poured into water by reaction after terminating, and is stood,
Layering, is extracted, organic phase uses NaHCO respectively with dichloromethane3The aqueous solution, distill water washing several times, organic phase rotary evaporation
Instrument concentrates, and removes the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 85%.With
Under be product nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR(400MHz,CDCl3) δ=8.22-8.24 (m, 1H), 8.05-8.07 (m, 1H), 7.78-7.80 (m,
2H),7.59-7.60(m,2H),7.49-7.51(m,2H),7.41-7.43(m,2H),7.35-7.37(m,2H),7.22-7.25
(m,2H),3.35(s,6H)ppm.
13C NMR (100MHz, CDCl3) δ=171.1,161.0,150.0,144.1,141.5,132.8,130.6,
129.2,128.8,127.9,127.2,126.5,125.9,125.4,124.8,124.0,123.5 122.8,121.7,
120.5,116.2,100.1,96.2ppm
HRMS m/z[M+H]+calcd:422.1271；found:422.1265.
Fluorescence quantum yield：0.70 (solution), 0.65 (solid-state)
Embodiment 6：
In 100mL reactors, 6- phenylacetylene bases -2- (2- pyridine radicals) -3- hydrogen quinazoline-4-ones 4.21g is added
(10mmol), it is solvent to add 50mL tetrahydrofurans, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), then adds
Entering the tetrahydrofuran solution of triphenyl borine, be heated to backflow, react 24h, reaction material liquid is poured into water by reaction after terminating,
Stand, layering, extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase rotates for the aqueous solution, distillation water washing
Evaporimeter concentrates, and removes the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield is
85%.It is nuclear magnetic resonance, Mass spectrometry experiments data and the fluorescence quantum yield of product below：
1H NMR(400MHz,CDCl3) δ=8.12-8.14 (m, 1H), 8.01-8.03 (m, 1H), 7.75-7.80 (m,
6H),7.56-7.57(m,2H),7.49-7.51(m,2H),7.41-7.47(m,6H),7.32-7.36(m,4H),7.21-7.23
(m,2H)ppm.
13C NMR (100MHz, CDCl3) δ=171.1,161.0,150.0,144.1,141.5,132.8,130.6,
129.2,128.8,128.5,128.2,128.0,127.8,127.4,126.8,126.0,125.5 124.8,123.7,
122.5,119.2ppm
HRMS m/z[M+H]+calcd:438.1772；found:438.1763.
Fluorescence quantum yield：0.56 (solution), 0.42 (solid-state)
Embodiment 7：
In 100mL reactors, 2- (2- pyridine radicals) -3- hydrogen quinazoline-4-one 2.23g (10mmol) are added, are added
50mL toluene is solvent, after being uniformly mixed, adds catechol 1.1g (10mmol), triethylamine 8.5mL (60mmol), connects
Addition BFEE compound, is heated to backflow, reacts 24h, reacts and reaction material liquid is poured into water after terminating
In, stand, layering, extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase is used for the aqueous solution, distillation water washing
Rotary Evaporators concentrate, and remove the mixture obtained after solvent, are separated using column chromatography chromatogram, obtained target product, yield
For 89%.It is nuclear magnetic resonance, Mass spectrometry experiments data and the fluorescence quantum yield of product below：
1H NMR (400MHz, DMSO-d6) δ=8.32-8.33 (m, 1H), 8.09-8.10 (m, 1H), 7.77-7.78 (m,
1H),7.62-7.63(m,1H),7.41-7.21(m,1H),7.35-7.31(m,1H),7.06-7.02(m,1H),6.65(d,J
=8Hz, 2H), 6.56 (d, J=8Hz, 2H) ppm.
13C NMR (100MHz, DMSO-d6) δ=171.9,162.41,154.6,149.7,145.6,140.9,137.8,
133.4,128.6,125.7,122.5 120.9,119.69,116.92,112.9,110.21ppm.
HRMS m/z[M+H]+calcd:342.1044；found:342.1052.
Fluorescence quantum yield：0.64 (solution), 0.10 (solid-state)
Embodiment 8：
In 100mL reactors, 2- (2- pyridine radicals) -3- hydrogen quinazoline-4-one 2.23g (10mmol) are added, are added
50mL toluene is solvent, after being uniformly mixed, adds salicylic acid 1.40g (10mmol), triethylamine 8.5mL (60mmol), connects
Addition BFEE compound, is heated to backflow, reacts 24h, reacts and reaction material liquid is poured into water after terminating
In, stand, layering, extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase is used for the aqueous solution, distillation water washing
Rotary Evaporators concentrate, and remove the mixture obtained after solvent, are separated using column chromatography chromatogram, obtained target product, yield
For 90%.It is nuclear magnetic resonance, Mass spectrometry experiments data and the fluorescence quantum yield of product below：
1H NMR (400MHz, DMSO-d6) δ=8.22-8.25 (m, 1H), 8.15-8.18 (m, 1H), 7.96-7.97 (m,
1H),7.85-7.89(m,1H),7.76-7.78(m,1H),7.54-7.58(m,1H),7.44-7.48(m,2H),7.05-7.07
(m,1H),6.95-7.03(m,3H)ppm.
13C NMR (100MHz, DMSO-d6) δ=174.1,170.2,164.2,147.8,145.6,135.5,133.5,
131.5,129.6,127.8,126.8,125.3,122.6,121.3,120.5,117.4,115.7,115.3,108.9,
102.6ppm.
HRMS[M+H]+calcd:370.0994；found:370.0102.
Fluorescence quantum yield：0.54 (solution), 0.12 (solid-state)
Embodiment 9：
In 100mL reactors, 2- (2- pyrrole radicals) -3- hydrogen quinazoline-4-one 2.11g (10mmol) are added, are added
50mL toluene is solvent, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into BFEE
Compound, backflow is heated to, reacts 24h, reaction material liquid is poured into water by reaction after terminating, and is stood, and layering, uses dichloromethane
Alkane extracts, and organic phase uses NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for the aqueous solution, distillation water washing
The mixture obtained after agent, is separated using column chromatography chromatogram, obtained target product, yield 75%.It is the core of product below
Magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR (400MHz, DMSO-d6) δ=8.12 (d, J=8Hz, 1H), 7.87-7.89 (m, 1H), 7.72 (d, J=
8Hz,1H),7.49-7.53(m,1H),7.45-7.41(m,1H),7.12-7.16(m,1H),6.32-6.30(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=172.3,156.9,144.9,136.9,136.4,135.7,134.7,
134.3,130.9,123.0,120.2,110.0ppm.
HRMS:m/z[M+H]+calcd:260.0801；found:260.0805.
Fluorescence quantum yield：0.74 (solution), 0.25 (solid-state)
Embodiment 10：
In 100mL reactors, 2- (6- propyl group -2- quinolyls) -3- hydrogen quinazoline-4-one 3.59g (10mmol) are added,
It is solvent to add 50mL toluene, after being uniformly mixed, adds catechol 1.1g (10mmol), triethylamine 8.5mL
(60mmol), BFEE compound is subsequently added into, is heated to backflow, react 24h, reaction will reaction after terminating
Feed liquid is poured into water, and is stood, and layering, is extracted with dichloromethane, organic phase uses NaHCO respectively3The aqueous solution, distillation water washing number
Time, organic phase is concentrated with Rotary Evaporators, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained mesh
Mark product, yield 89%.It is nuclear magnetic resonance, Mass spectrometry experiments data and the fluorescence quantum yield of product below：
1H NMR (400MHz, DMSO-d6) δ=10.5 (br s, 2H), 8.42-8.43 (m, 1H), 8.05-8.06 (m,
1H),7.72-7.74(m,1H),7.65-7.66(m,1H),7.41-7.42(m,2H),7.30-7.31(m,2H),7.06-7.08
(m,1H),2.62-2.64(m,2H),1.65-1.67(m,2H),0.92-0.94(m,3H)ppm.
13C NMR (100MHz, DMSO-d6) δ=170.5,160.2,151.4,145.6,142.7,130.8,130.1,
129.5,128.6,127.1,126.5,125.3,124.7,123.3,122.5,121.1,118.4,28.3,19.6,
12.5ppm.
HRMS m/z[M+H]+calcd:360.1514；found:360.1519.
Fluorescence quantum yield：0.24 (solution), 0.20 (solid-state)
Embodiment 11：
In 100mL reactors, 2- (2- indyls) -3- hydrogen quinazoline-4-one 2.61g (10mmol) are added, are added
50mL toluene is solvent, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into BFEE
Compound, backflow is heated to, reacts 24h, reaction material liquid is poured into water by reaction after terminating, and is stood, and layering, uses dichloromethane
Alkane extracts, and organic phase uses NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for the aqueous solution, distillation water washing
The mixture obtained after agent, is separated using column chromatography chromatogram, obtained target product, yield 70%.It is the core of product below
Magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR(400MHz,CDCl3) δ=8.5 (br s, 1H), 7.91-7.92 (m, 1H), 7.70-7.71 (m, 1H),
7.45-7.48(m,1H),7.33-7.35(m,2H),7.26-7.28(m,3H),7.11-7.13(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=175.2,163.98,147.68,146.9,136.2,133.85,
128.6,127.78,126.93,122.4,121.8,120.6,117.98,115.58,115.17,102.6ppm.
HRMS:[M+H]+calcd:310.0958；found:310.0967.
Fluorescence quantum yield：0.84 (solution), 0.35 (solid-state)
Embodiment 12：
In 100mL reactors, 2- (2-[4-morpholinodithio base) -3- hydrogen quinazoline-4-one 2.79g (10mmol) are added, are added
It is solvent to enter 50mL toluene, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second
Ether compound, backflow is heated to, reacts 24h, reaction material liquid is poured into water by reaction after terminating, and is stood, and layering, uses dichloro
Methane extracts, and organic phase uses NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for the aqueous solution, distillation water washing
The mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 95%.It is product below
Nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR(400MHz,CDCl3) δ=8.23-8.25 (m, 1H), 7.95-7.96 (m, 1H), 7.63-7.59 (m,
2H),7.48-7.45(m,3H),7.34-7.35(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=176.1,163.98,156.3,152.9,147.68,146.92,
133.8,130.5 127.7,126.9,122.6,122.1 117.9,115.5,115.1ppm.
HRMS(ESI):m/z[M+H]+calcd:328.0522；found:328.0525.
Fluorescence quantum yield：0.90 (solution), 0.60 (solid-state)
Embodiment 13：
In 100mL reactors, 2- (2- quinazolyls) -3- hydrogen quinazoline-4-one 2.79g (10mmol) are added, are added
50mL toluene is solvent, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into BFEE
Compound, backflow is heated to, reacts 24h, reaction material liquid is poured into water by reaction after terminating, and is stood, and layering, uses dichloromethane
Alkane extracts, and organic phase uses NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for the aqueous solution, distillation water washing
The mixture obtained after agent, is separated using column chromatography chromatogram, obtained target product, yield 86%.It is the core of product below
Magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR (400MHz, DMSO-d6) δ=9.50 (s, 1H), 8.42-8.43 (m, 1H), 7.85-7.86 (m, 2H),
7.66-7.68(m,2H),7.62-7.58(m 1H),7.26-7.23(m,1H),6.76(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=178.1,165.5,163.7,156.2,150.0,147.7,133.9,
132.8,128.2,127.8,122.1,119.0,117.0,115.7,114.9,111.9ppm.
HRMS(ESI):m/z[M+H]+calcd:323.0910；found:323.0915.
Fluorescence quantum yield：0.84 (solution), 0.43 (solid-state)
Embodiment 14：
In 100mL reactors, 2- (6- nitro -2- quinazolyls) -3- hydrogen quinazoline-4-ones 3.67g is added
(10mmol), it is solvent to add 50mL toluene, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), is subsequently added into three
Boron fluoride ether complex, backflow being heated to, react 24h, reaction material liquid is poured into water by reaction after terminating, and is stood,
Layering, is extracted, organic phase uses NaHCO respectively with dichloromethane3The aqueous solution, distill water washing several times, organic phase rotary evaporation
Instrument concentrates, and removes the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 86%.With
Under be product nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR (400MHz, DMSO-d6) δ=9.50 (s, 1H), 8.72-8.73 (m, 2H), 8.21-8.23 (m, 1H),
7.76-7.78(m,2H),7.65-7.67(m 1H),7.36-7.35(m,1H),7.21-7.23(m,1H)ppm.
13C NMR (100MHz, DMSO-d6) δ=178.1,170.5,167.7,159.8,155.0,149.7,142.9,
138.8, 135.2,133.8,129.5,128.1,126.0,125.3,124.4,120.8.ppm.
HRMS(ESI):m/z[M+H]+calcd:368.0761；found:368.0753.
Fluorescence quantum yield：0.34 (solution), 0.12 (solid-state)
Embodiment 15：
In 100mL reactors, 6- methoxyl groups -2- (6- cyano group -2- quinazolyls) -3- hydrogen quinazoline-4-ones are added
3.72g (10mmol), it is solvent to add 50mL toluene, after being uniformly mixed, adds triethylamine 8.5mL (60mmol), then
Boric acid is added, is heated to backflow, reacts 24h, reaction material liquid is poured into water by reaction after terminating, and is stood, and layering, uses dichloro
Methane extracts, and organic phase uses NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for the aqueous solution, distillation water washing
The mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield 86%.It is product below
Nuclear magnetic resonance, Mass spectrometry experiments data and fluorescence quantum yield：
1H NMR (400MHz, DMSO-d6) δ=10.5 (br s, 2H), 8.36-8.38 (m, 1H), 8.10-8.11 (m,
1H),7.80-7.81(m,1H),7.62-7.63(m,1H),7.39-7.40(m,1H),7.30-7.31(m,2H),7.01-7.02
(m,1H),3.85(s,3H)ppm.
13C NMR (100MHz, DMSO-d6) δ=171.5,161.2,152.4,146.6,143.7,131.8,131.1,
129.8,128.6,128.1,127.5,126.3,125.7,124.3,123.5,122.1,119.4,118.5,56.2ppm
HRMS(ESI):m/z[M+H]+calcd:373.1103；found:373.1109.
Fluorescence quantum yield：0.36 (solution), 0.30 (solid-state).
Claims (5)
- The quinazolinone boride of 1.2- nitrogen heteroaromatic rings substitution, has such as following formula I or the general structure of formula II：Wherein, nitrogen heteroaromatic rings (A rings) are selected from：Pyrroles, pyridine, quinoline, indoles, thiazole, oxazole, imidazoles, benzothiazole, benzo are disliked Azoles, benzimidazole, pyridazine, pyrazine, pyrimidine, quinoxaline, purine etc.；Functional group X is selected from：Halogen atom, alkynyl, phenyl, substituted-phenyl, hydroxyl, alkyl, alkoxy, phenol epoxide, substituted phenol oxygen The groups such as base, cyano group, adjacent diphenol epoxide, the adjacent diphenol epoxide of substitution, salicylate, substituted salicylic acid root；R1It is selected from：Alkyl, halogen atom, alkenyl, alkynyl, phenyl, substituted-phenyl, aryl, substituted aryl, hydroxyl, alkoxy, phenol Epoxide, acyl group, aldehyde radical, carboxyl, amide groups, nitro, amino, substituted-amino, heterocyclic radical, substituted heterocyclic radical, cyano group, sulfonic group, The groups such as sulfydryl, alkylthio group；R2It is selected from：Alkyl (including cycloalkyl), alkyl heterocycle, halogen atom, alkenyl, alkynyl, phenyl, substituted-phenyl, aryl, take For aryl, hydroxyl, alkoxy, phenol epoxide, acyl group, aldehyde radical, carboxyl, amide groups, nitro, amino, substituted-amino, heterocyclic radical, take For groups such as heterocyclic radical, cyano group, sulfonic group, sulfydryl, alkylthio groups.
- 2. the preparation method of the quinazolinone boride of 2- nitrogen heteroaromatic rings substitution according to claim 1, including following step Suddenly：(1) two nitrogen ligands (or corresponding derivative) of a certain amount of Quinazolinone-containing construction unit are added, in non-polar solven, The raw materials such as corresponding boride and catechol, salicylic acid are added according to specific reaction therebetween, with triethylamine adjust reaction solution to Alkalescence, back flow reaction 24 hours；(2) reaction material liquid is poured into water, stood, layering, extracted with dichloromethane, organic phase uses NaHCO respectively3The aqueous solution, steaming Distilled water is washed several times, and organic phase is concentrated with Rotary Evaporators, removes the mixture obtained after solvent, utilizes column chromatography chromatogram point From obtained sterling.
- 3. preparation method according to claim 2, it is characterised in that：The phenodiazine of described Quinazolinone-containing construction unit is matched somebody with somebody Body (or corresponding derivative), there is the structure such as following formula III or formula IV：Wherein, nitrogen heteroaromatic rings (A rings) are selected from：Pyrroles, pyridine, quinoline, indoles, thiazole, oxazole, imidazoles, benzothiazole, benzo are disliked Azoles, benzimidazole, pyridazine, pyrazine, pyrimidine, quinoxaline, purine etc.；R1And R2It is selected from：Alkyl (including cycloalkyl), alkyl heterocycle, halogen atom, alkenyl, alkynyl, phenyl, substituted-phenyl, virtue Base, substituted aryl, hydroxyl, alkoxy, phenol epoxide, acyl group, aldehyde radical, carboxyl, amide groups, nitro, amino, substituted-amino, heterocycle The groups such as base, substituted heterocyclic radical, cyano group, sulfonic group, sulfydryl, alkylthio group.
- 4. preparation method according to claim 2, it is characterised in that：Described boride is that BFEE is compound Thing, boric acid, triphenyl borine or tri-substituted phenyl boron.
- 5. application of the quinazolinone boride of 2- nitrogen heteroaromatic rings substitution according to claim 1 in fluorescent material.
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Cited By (7)
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|---|---|---|---|---|
| CN109503550A (en) * | 2018-11-20 | 2019-03-22 | 江西师范大学 | 2- azepine aryl-6-substituted-amino quinazolinones and its preparation method and application |
| CN109694372A (en) * | 2018-12-11 | 2019-04-30 | 湖南大学 | A kind of two-photon fluorescence probe and the preparation method and application thereof |
| CN113461914A (en) * | 2021-06-21 | 2021-10-01 | 上饶师范学院 | D-pi-A type polymer fluorescent material containing 2, 6-diphenyl-4-aryl pyridine structure and synthetic method thereof |
| CN113583031A (en) * | 2021-07-06 | 2021-11-02 | 江西师范大学 | Endoplasmic reticulum positioning imaging/photoinduced iron death dual-function probe |
| CN113980039A (en) * | 2021-11-19 | 2022-01-28 | 杭州师范大学 | Photothermal agent and preparation method and application thereof |
| CN115850308A (en) * | 2022-11-07 | 2023-03-28 | 淮阴工学院 | BODIPY near-infrared fluorescent probe containing electron donor and acceptor group recognition Abeta fibers and preparation method thereof |
| CN116003448A (en) * | 2022-11-07 | 2023-04-25 | 淮阴工学院 | BODIPY near infrared fluorescent probe containing indoline polyethylenically recognized Abeta fiber and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503550A (en) * | 2018-11-20 | 2019-03-22 | 江西师范大学 | 2- azepine aryl-6-substituted-amino quinazolinones and its preparation method and application |
| CN109503550B (en) * | 2018-11-20 | 2022-11-29 | 江西师范大学 | 2-azaaryl-6-substituted amino quinazolinone compound and preparation method and application thereof |
| CN109694372A (en) * | 2018-12-11 | 2019-04-30 | 湖南大学 | A kind of two-photon fluorescence probe and the preparation method and application thereof |
| CN109694372B (en) * | 2018-12-11 | 2021-08-24 | 湖南大学 | Two-photon fluorescent probe and preparation method and application thereof |
| CN113461914A (en) * | 2021-06-21 | 2021-10-01 | 上饶师范学院 | D-pi-A type polymer fluorescent material containing 2, 6-diphenyl-4-aryl pyridine structure and synthetic method thereof |
| CN113583031B (en) * | 2021-07-06 | 2022-07-26 | 江西师范大学 | Endoplasmic reticulum positioning imaging/photoinduced iron death dual-function probe |
| CN113583031A (en) * | 2021-07-06 | 2021-11-02 | 江西师范大学 | Endoplasmic reticulum positioning imaging/photoinduced iron death dual-function probe |
| CN113980039A (en) * | 2021-11-19 | 2022-01-28 | 杭州师范大学 | Photothermal agent and preparation method and application thereof |
| CN113980039B (en) * | 2021-11-19 | 2023-08-18 | 杭州师范大学 | Photothermal agent and preparation method and application thereof |
| CN115850308A (en) * | 2022-11-07 | 2023-03-28 | 淮阴工学院 | BODIPY near-infrared fluorescent probe containing electron donor and acceptor group recognition Abeta fibers and preparation method thereof |
| CN116003448A (en) * | 2022-11-07 | 2023-04-25 | 淮阴工学院 | BODIPY near infrared fluorescent probe containing indoline polyethylenically recognized Abeta fiber and preparation method thereof |
| CN116003448B (en) * | 2022-11-07 | 2024-06-11 | 淮阴工学院 | BODIPY near infrared fluorescent probe containing indoline polyethylenically recognized Abeta fiber and preparation method thereof |
| CN115850308B (en) * | 2022-11-07 | 2024-06-11 | 淮阴工学院 | BODIPY near infrared fluorescent probe containing electron donor and acceptor groups for recognizing Abeta fibers and preparation method thereof |
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