CN107857773B - The quinazolinone boride that 2- nitrogen heteroaromatic rings replace - Google Patents
The quinazolinone boride that 2- nitrogen heteroaromatic rings replace Download PDFInfo
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- CN107857773B CN107857773B CN201710088903.3A CN201710088903A CN107857773B CN 107857773 B CN107857773 B CN 107857773B CN 201710088903 A CN201710088903 A CN 201710088903A CN 107857773 B CN107857773 B CN 107857773B
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- quinazolinone
- hydrogen quinazoline
- boride
- reaction
- heteroaromatic rings
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical compound C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 55
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 48
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- -1 2- quinolyl Chemical group 0.000 claims description 32
- 239000012074 organic phase Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- QMNUDYFKZYBWQX-UHFFFAOYSA-N 1H-quinazolin-4-one Chemical compound C1=CC=C2C(=O)N=CNC2=C1 QMNUDYFKZYBWQX-UHFFFAOYSA-N 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 18
- 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
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 14
- 229910015900 BF3 Inorganic materials 0.000 claims description 14
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- 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
- 239000012454 non-polar solvent Substances 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
- 240000000203 Salix gracilistyla Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000012153 distilled water Substances 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052796 boron Inorganic materials 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000003814 drug Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 abstract 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical compound C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000049 pigment Substances 0.000 abstract 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 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
- 238000005481 NMR spectroscopy Methods 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 15
- 238000004949 mass spectrometry Methods 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 15
- 238000004821 distillation Methods 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000003963 dichloro group Chemical group Cl* 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 238000000034 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
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002428 photodynamic therapy Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 2
- 229960004889 salicylic acid Drugs 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-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
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 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
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002475 indoles Chemical class 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
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 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
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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
- 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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- 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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- 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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- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to a kind of novel efficient organic fluorescence molecules --- and the quinazolinone boride that 2- nitrogen heteroaromatic rings replace, the quinazolinone boride which replaces can be Material synthesis by the quianzolinones and boron-containing compound that 2- nitrogen heteroaromatic rings replace.Since the quinazolinone parent that 2- nitrogen heteroaromatic rings replace can introduce other groups, by being reacted from different borides, novel material of fluoran fuctional pigments can be synthesized, such as introduce conjugation aromatic rings or aromatic heterocycle, conjugated system can be made to increase, or introduce electron donating group such as triphenylamine, diethylamine etc., keep the launch wavelength of these compounds mobile to long wave direction, and then obtain novel, the fluorescent molecule with various launch wavelengths.Fluorescent material prepared by this molecule will be widely used in the fields such as luminous and display device, chemical industry, biological medicine, pesticide, military project, intelligent terminal.
Description
Technical field
The present invention relates to Functional dye fields, and in particular to a kind of novel luminescent organic molecule --- 2- nitrogen heteroaromatic rings take
The quinazolinone boride in generation.
Background technique
The multiple color and excellent luminescent properties and unique processing that functional organic pigment molecule can be presented with it
Performance, can convenient adjusting molecular structure, for a long time by the favor of researcher, and light emitting diode, solar battery, field imitate
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 the research 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 can effectively adjust its Photophysics, while boracic organic compound also has special chemical stability.Especially four
The organic B complex of corrdination type, luminescent properties are superior, since its high molar absorption coefficient, good photostability and chemistry are steady
It is qualitative, it is 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, and purifying is complex, especially classical BODIPY type boracic complex dye point
Son.
By two nitrogen ligands of Quinazolinone-containing structural unit, (or it is corresponding derivative by simple synthesis step by the present invention
Object) it is coordinated with boron, the quinazolinone boride that a kind of novel 2- nitrogen heteroaromatic rings replace is obtained, is a kind of novel organic hair
Luminescent material.In this way, can effective conjugated system in further expansion quinazolinone molecular structure, realize and improve material
Luminous efficiency itself adjusts launch wavelength, or even changes illumination mode, extends the purpose of luminescent lifetime.Due to the boron after coordination
Complex space structure is X-type, can inhibit 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.
Summary of the invention
The purpose of the present invention is to provide a kind of novel luminescent organic molecules --- the quinazolinone that 2- nitrogen heteroaromatic rings replace
Boride and preparation method thereof.
The quinazolinone boride that a kind of 2- nitrogen heteroaromatic rings replace has the general structure such as following formula I or formula II:
Wherein, nitrogen heteroaromatic rings (A ring) can be with are as follows: 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 oxygroup, substitution
Phenol oxygroup, adjacent diphenol oxygroup, replaces the groups such as adjacent diphenol oxygroup, salicylate, substituted salicylic acid root at cyano.
R1~R2 can for alkyl, halogen atom, alkenyl, alkynyl, phenyl, substituted-phenyl, aryl, substituted aryl, hydroxyl,
Alkoxy, phenol oxygroup, acyl group, aldehyde radical, carboxyl, amide groups, nitro, amino, substituted-amino, heterocycle, substituted heterocyclic radical, cyanogen
The groups such as base, sulfonic group, sulfydryl, alkylthio group.
The quinazolinone boride that above-mentioned 2- nitrogen heteroaromatic rings replace can by Quinazolinone-containing structural unit two nitrogen ligands (or
Its corresponding derivative) with boron compound be Material synthesis.
The preparation method for the quinazolinone boride that above-mentioned 2- nitrogen heteroaromatic rings replace:
In the round-bottomed flask being protected from light, two nitrogen ligands that a certain amount of Quinazolinone-containing structural unit is added (or accordingly spread out
Biology), in nonpolar solvent, corresponding boride is added according to specific reaction therebetween in back flow reaction several hours.Use high pressure
Liquid chromatogram (HPLC) and thin-layer chromatography (TLC) track entire reaction process, judge reaction end.After reaction terminating, reaction solution
After the processing such as washed, extraction, obtained extract liquor is concentrated with Rotary Evaporators, removes the mixture obtained after solvent, is utilized
Column chromatography chromatogram separation, 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 product structure.
The fluorescence property measurement for the quinazolinone boride that this kind of 2- nitrogen heteroaromatic rings replace, mainly comprises the steps that
(1) product is dissolved in acetonitrile solvent, is configured to a certain concentration, determine compound most using Fluorescence Spectrometer
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 Fluorescence Spectrometer, 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 that this kind of 2- nitrogen heteroaromatic rings replace can be used to prepare highly efficient fluorescent material, preparation it is efficient
Fluorescent material has many advantages, such as that property is stable, save the convenient, visibility of material and brightness is high.
Beneficial effects of the present invention: the quinazolinone boride and other existing boron that 2- nitrogen heteroaromatic rings of the invention replace
Compound, which is compared, has fluorescence quantum efficiency height, all has the preferable characteristics of luminescence, synthesis under solution and solid-state two states
It is easy, yield is higher, can be the gram-grade even feather weight large-scale production the advantages that；It is introduced by group, the launch wavelength of compound
Can be mobile to long wave direction, and then obtain novel, the fluorescent molecule with various launch wavelengths, these molecules can be used for preparing
Highly efficient fluorescent material；Preparation method of the invention is simple, raw material is easy to get, yield is higher, and therefore, this novel compound can answer
It for fields such as luminous and display device, chemical industry, biological medicine, pesticide, military project, intelligent terminals, and is China in functional material
A kind of novel fluorescent material is developed in field.
Detailed description of the invention
Fig. 1 is quinazolinone boron compound prepared by example 11H NMR spectra.
Fig. 2 is quinazolinone boron compound prepared by example 113C NMR spectra.
Fig. 3 is the crystal structure figure of 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.
Specific embodiment
Below with reference to specific example, the present invention is further elaborated, but patent right is not limited to these embodiments.
Embodiment 1:
In 100mL reactor, the bromo- 2- of 6- (2- pyridyl group) -3- hydrogen quinazoline-4-one 3.50g (10mmol) is added, adds
Entering 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second
Ether compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloro is used in layering
Methane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for 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 product prepared by embodiment 1:
Embodiment 2:
In 100mL reactor, 2- (2- quinolyl) -3- hydrogen quinazoline-4-one 3.21g (10mmol) is added, is added
50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride ether
Compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloromethane is used in layering
Alkane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for 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 reactor, the bromo- 2- of 6- (2- pyridyl group) -3- hydrogen quinazoline-4-one 4.00g (10mmol) is added, adds
Entering 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second
Ether compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloro is used in layering
Methane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for 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 reactor, 6- dimethylamino -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 3.64g is added
(10mmol), addition 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into three
Boron fluoride ether complex is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands,
Layering, is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous solution distills water washing several times, organic phase rotary evaporation
Instrument concentration, is removed 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 reactor, 6- phenylacetylene base -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 4.21g is added
(10mmol), addition 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into three
Boron fluoride ether complex is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands,
Layering, is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous solution distills water washing several times, organic phase rotary evaporation
Instrument concentration, is removed 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 reactor, 6- phenylacetylene base -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 4.21g is added
(10mmol), addition 50mL tetrahydrofuran be solvent, after being uniformly mixed, be added triethylamine 8.5mL (60mmol), then plus
The tetrahydrofuran solution for entering triphenyl borine is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction,
It stands, layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase rotates for aqueous solution, distillation water washing
Evaporimeter concentration, is removed 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 reactor, 2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 2.23g (10mmol) is added, is added
50mL toluene is solvent, after being uniformly mixed, is added catechol 1.1g (10mmol), triethylamine 8.5mL (60mmol) connects
Addition boron trifluoride ether compound, be heated to reflux, reaction material liquid for 24 hours, is poured into water after reaction by reaction
In, it stands, layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase is used for aqueous solution, distillation water washing
Rotary Evaporators concentration, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield
It is 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 reactor, 2- (2- pyridyl group) -3- hydrogen quinazoline-4-one 2.23g (10mmol) is added, is added
50mL toluene is solvent, after being uniformly mixed, is added salicylic acid 1.40g (10mmol), triethylamine 8.5mL (60mmol) connects
Addition boron trifluoride ether compound, be heated to reflux, reaction material liquid for 24 hours, is poured into water after reaction by reaction
In, it stands, layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Several times, organic phase is used for aqueous solution, distillation water washing
Rotary Evaporators concentration, is removed the mixture obtained after solvent, is separated using column chromatography chromatogram, obtained target product, yield
It is 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 reactor, 2- (2- pyrrole radicals) -3- hydrogen quinazoline-4-one 2.11g (10mmol) is added, is added
50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride ether
Compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloromethane is used in layering
Alkane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for 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:
1δ=8.12 (d, J=8Hz, 1H) H NMR (400MHz, DMSO-d6), 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 reactor, 2- (6- propyl -2- quinolyl) -3- hydrogen quinazoline-4-one 3.59g (10mmol) is added,
Addition 50mL toluene is solvent, after being uniformly mixed, is added catechol 1.1g (10mmol), triethylamine 8.5mL
(60mmol) is subsequently added into boron trifluoride ether compound, is heated to reflux, and reaction for 24 hours, after reaction will reaction
Feed liquid is poured into water, and is stood, and layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous 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:
1δ=10.5 H NMR (400MHz, DMSO-d6) (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 reactor, 2- (2- indyl) -3- hydrogen quinazoline-4-one 2.61g (10mmol) is added, is added
50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride ether
Compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloromethane is used in layering
Alkane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for 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 reactor, 2- (2-[4-morpholinodithio base) -3- hydrogen quinazoline-4-one 2.79g (10mmol) is added, adds
Entering 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride second
Ether compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloro is used in layering
Methane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for 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 reactor, 2- (2- quinazolyl) -3- hydrogen quinazoline-4-one 2.79g (10mmol) is added, is added
50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into boron trifluoride ether
Compound is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands, and dichloromethane is used in layering
Alkane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed molten for 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:
1δ=9.50 (s, 1H) H NMR (400MHz, DMSO-d6), 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 reactor, 2- (6- nitro -2- quinazolyl) -3- hydrogen quinazoline-4-one 3.67g is added
(10mmol), addition 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), is subsequently added into three
Boron fluoride ether complex is heated to reflux, and reaction material liquid for 24 hours, is poured into water by reaction after reaction, stands,
Layering, is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous solution distills water washing several times, organic phase rotary evaporation
Instrument concentration, is removed 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:
1δ=9.50 (s, 1H) H NMR (400MHz, DMSO-d6), 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 reactor, 6- methoxyl group -2- (6- cyano -2- quinazolyl) -3- hydrogen quinazoline-4-one is added
3.72g (10mmol), addition 50mL toluene is solvent, after being uniformly mixed, is added triethylamine 8.5mL (60mmol), then
Boric acid is added, is heated to reflux, reaction material liquid for 24 hours, is poured into water by reaction after reaction, is stood, and dichloro is used in layering
Methane extraction, organic phase use NaHCO respectively3Several times, organic phase is concentrated with Rotary Evaporators, is removed for 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:
1δ=10.5 H NMR (400MHz, DMSO-d6) (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 (4)
- The quinazolinone boride that 1.2- nitrogen heteroaromatic rings replace has the structure as shown in any structure formula in following structural:
- 2. the preparation method for the quinazolinone boride that 2- nitrogen heteroaromatic rings according to claim 1 replace, including following step It is rapid:(1) two nitrogen ligands or corresponding derivative of a certain amount of Quinazolinone-containing structural unit are added, in nonpolar solvent, Between corresponding boride and catechol, bigcatkin willow acid starting material be added according to specific reaction, adjust reaction solution to alkalinity with triethylamine, Back flow reaction 24 hours；(2) reaction material liquid is poured into water, is stood, layering is extracted with dichloromethane, organic phase uses NaHCO respectively3Aqueous 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；Wherein, two nitrogen ligands of the Quinazolinone-containing structural unit or corresponding derivative areThe bromo- 2- of 6- (2- pyridyl group) -3- hydrogen quinazoline-4-one,2- (2- quinolyl) -3- hydrogen quinazoline-4-one,The bromo- 2- of 6- (2- pyridyl group) -3- hydrogen quinazoline-4-one,6- dimethylamino -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,6- phenylacetylene base -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,6- phenylacetylene base -2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,2- (2- pyridyl group) -3- hydrogen quinazoline-4-one,2- (2- pyrrole radicals) -3- hydrogen quinazoline-4-one,2- (6- propyl -2- quinolyl) -3- hydrogen quinazoline-4-one,2- (2- indyl) -3- hydrogen quinazoline-4-one,2- (2-[4-morpholinodithio base) -3- hydrogen quinazoline-4-one,2- (2- quinazolyl) -3- hydrogen quinazoline-4-one,2- (6- nitro -2- quinazolyl) -3- hydrogen quinazoline-4-one, or6- methoxyl group -2- (6- cyano -2- quinazolyl) -3- hydrogen quinazoline-4-one.
- 3. preparation method according to claim 2, it is characterised in that: the boride is that boron trifluoride ether is compound Object, boric acid or triphenyl borine.
- 4. application of the quinazolinone boride that 2- nitrogen heteroaromatic rings according to claim 1 replace in fluorescent material.
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| CN113583031B (en) * | 2021-07-06 | 2022-07-26 | 江西师范大学 | Endoplasmic reticulum positioning imaging/photoinduced iron death dual-function probe |
| CN113980039B (en) * | 2021-11-19 | 2023-08-18 | 杭州师范大学 | Photothermal agent and preparation method and application 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 |
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