CN103508940B - 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates - Google Patents

6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates Download PDF

Info

Publication number
CN103508940B
CN103508940B CN201310250838.1A CN201310250838A CN103508940B CN 103508940 B CN103508940 B CN 103508940B CN 201310250838 A CN201310250838 A CN 201310250838A CN 103508940 B CN103508940 B CN 103508940B
Authority
CN
China
Prior art keywords
compound
yield
reaction
white solid
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201310250838.1A
Other languages
Chinese (zh)
Other versions
CN103508940A (en
Inventor
邱勇
范洪涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
Original Assignee
Tsinghua University
Beijing Visionox Technology Co Ltd
Kunshan Visionox Display Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tsinghua University, Beijing Visionox Technology Co Ltd, Kunshan Visionox Display Co Ltd filed Critical Tsinghua University
Priority to CN201310250838.1A priority Critical patent/CN103508940B/en
Publication of CN103508940A publication Critical patent/CN103508940A/en
Application granted granted Critical
Publication of CN103508940B publication Critical patent/CN103508940B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/16—Preparation of halogenated hydrocarbons by replacement by halogens of hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/18—Polycyclic aromatic halogenated hydrocarbons
    • C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D217/00—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems
    • C07D217/02—Heterocyclic compounds containing isoquinoline or hydrogenated isoquinoline ring systems with only hydrogen atoms or radicals containing only carbon and hydrogen atoms, directly attached to carbon atoms of the nitrogen-containing ring; Alkylene-bis-isoquinolines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
    • C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
    • C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
    • C07D271/107—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles with two aryl or substituted aryl radicals attached in positions 2 and 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62—Benzothiazoles
    • C07D277/64—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2
    • C07D277/66—Benzothiazoles with only hydrocarbon or substituted hydrocarbon radicals attached in position 2 with aromatic rings or ring systems directly attached in position 2
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/623—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing five rings, e.g. pentacene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565—Oxadiazole compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Indole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

The invention relates to a compound represented by formula (1). When R5 and R6 both represent H, then R7 and R8 are independently selected from C5-C30 nitrogen heterocyclic ring, substituted nitrogen heterocyclic ring or condensed heterocyclic aromatic hydrocarbon containing nitrogen; and R1 and R2 are independently selected from C1-C30 linear hydrocarbon or branched-chain hydrocarbon, C6-C30 substituted or unsubstituted benzene ring or polycyclic aromatic hydrocarbon; or R1 and R2 represent cyclic compounds formed by connection with other groups. Or when R7 and R8 both represent H, then R5 and R6 are independently selected from C5-C30 nitrogen heterocyclic ring, substituted nitrogen heterocyclic ring or condensed heterocyclic aromatic hydrocarbon containing nitrogen; and R1 and R2 are independently selected from C1-C30 linear hydrocarbon or branched-chain hydrocarbon, C6-C30 substituted or unsubstituted benzene ring or polycyclic aromatic hydrocarbon; or R1 and R2 represent cyclic compounds formed by connection with other groups. The invention also discloses applications of the 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates in organic light-emitting devices (OLED), and especially applications of the 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates as electron transport materials, and fluorescence or red phosphorescence host materials in OLED.

Description

6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative, intermediate, preparation method and application
Technical Field
The invention relates to an organic compound, in particular to a compound for an organic electroluminescent device, a preparation method thereof and application of the compound in the organic electroluminescent device; the invention also relates to an intermediate of the compound and a preparation method of the intermediate.
Background
The electroluminescence phenomenon was originally discovered in the thirties of the 20 th century, and the initial luminescent material was ZnS powder, so LED technology was developed and now widely applied to energy-saving light sources. The organic electroluminescence phenomenon is the earliest discovery of Pope et al in 1963, and the organic electroluminescence phenomenon shows that a single-layer crystal of anthracene can emit weak blue light under the driving of a voltage of more than 100V. Until 1987, Rooibos, Dengqing cloud, et al, from Kodak corporation, made organic fluorescent dyes into double-layer devices by vacuum evaporation, the external quantum efficiency reached 1% at a driving voltage less than 10V, so that organic electroluminescent materials and devices have the possibility of practicability, and the research on OLED materials and devices was greatly promoted.
Compared with inorganic luminescent materials, organic electroluminescent materials have the following advantages: 1. the organic material has good processing performance, and can form a film on any substrate by a method of evaporation or spin coating; 2. the diversity of the organic molecular structure can adjust the thermal stability, mechanical property, luminescence and conductivity of the organic material by the method of molecular structure design and modification, so that the material has great improvement space.
The light emitting principle of organic electroluminescent diodes is similar to that of inorganic light emitting diodes. When the element is subjected to forward bias derived from direct current, the applied voltage energy injects driving electrons (electrons) and holes (holes) into the element from the cathode and the anode respectively, when the electrons and the holes meet and combine in the light-emitting layer, so-called Electron-Hole composite excitons are formed, and the excitons return to the ground state in a light-emitting relaxation mode, so that the purpose of light emission is achieved.
Organic electroluminescence is generated by recombination of carriers (electrons and holes) transported in an organic semiconductor material, which is known to have poor conductivity, unlike inorganic semiconductors, where there is no continuous energy band, and the transport of carriers is described by the hopping theory, i.e., electrons are excited or injected into the LUMO level of a molecule under the driving of an electric field, and reach the purpose of charge transport by hopping to the LUMO level of another molecule. In order to make organic electroluminescent devices breakthrough in application, the difficulties of poor charge injection and transport capabilities of organic materials must be overcome. Scientists have been able to adjust the device structure, such as increasing the number of organic material layers of the device, and making different organic layers play different roles, such as some functional materials assisting the injection of electrons from the cathode and holes from the anode, some materials assisting the transport of charges, some materials blocking the transport of electrons and holes, and certainly the most important luminescent materials of various colors in organic electroluminescence should also achieve the purpose of matching with the adjacent functional materials.
Common functionalized organic materials are: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, and light emitting host materials and light emitting objects (dyes), and the like.
Hole Injection Materials (HIM) require a HOMO level between the anode and the hole transport layer, which is beneficial for increasing hole injection between interfaces, and common hole injection materials are CuPc, TNATA, and PEDT: PSS, and the like.
The Hole Transport Material (HTM) is required to have high thermal stability (high Tg), have a small barrier against an anode or a hole injection material, have high hole transport ability, and be capable of forming a pinhole-free thin film by vacuum evaporation. The commonly used HTMs are aromatic polyamine compounds, mainly triarylamine derivatives, such as: NPB (T)g=98℃,μh=1×10-3cm2V-1s-1）,TPD（Tg=60℃,μh=1×10-3cm2V-1s-1），TCTA（Tg=151℃,μh=1.5×10-4cm2V-1s-1For blue phosphorescent OLEDs), DTASi (T)g=106℃,μh=1×10-3cm2V-1s-1For blue phosphorescent OLEDs), etc.
Electron Transport Materials (ETM) require that the ETM have a reversible and sufficiently high electrochemical reduction potential, that the appropriate HOMO and LUMO energy levels allow for better Electron injection, and that it preferably have hole blockingGear shifting capacity; high electron transmission capacity, good film forming property and thermal stability. ETM is generally a conjugated planar aromatic compound with an electron-deficient structure. A common electron transport material is AlQ3（μe=5×10-6cm2V-1s-1）、Bphen（μe=4×10-4cm2V-1s-1）、BCP(LUMO=3.0eV，μe=1.1×10-3cm2V-1s-1)、PBD（μe=1.9×10-5cm2V-1s-1) And the like.
The light-emitting layer host material (host) needs to have the following characteristics: reversible electrochemical redox potential, HOMO and LUMO energy levels matched with adjacent hole and electron transport layers, good and matched hole and electron transport capacity, good high thermal stability and film forming properties, and appropriate singlet or triplet energy gaps for controlling excitons in the light emitting layer, as well as good energy transfer with corresponding fluorescent or phosphorescent dyes.
The luminescent material of the luminescent layer needs to have the following characteristics: has high fluorescence or phosphorescence quantum efficiency; the absorption spectrum of the dye has good overlap with the emission spectrum of the main body, namely the main body is matched with the energy of the dye, and the energy can be effectively transferred from the main body to the dye; the emission peaks of red, green and blue are as narrow as possible to obtain good color purity; good stability, and can be used for vapor deposition.
Disclosure of Invention
The invention aims to provide an organic material which can be used for an electron transport layer and a luminescent layer of an organic electroluminescent device, and the invention adopts the following scheme:
a6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative has a structure shown in formula (1):
wherein:
when R is5、R6While being H, R7、R8Are each independently selected from C5-C30A nitrogen-containing heterocycle, a substituted nitrogen heterocycle or a fused nitrogen-containing heterocyclic aromatic hydrocarbon of
R1、R2Each independently selected from the group consisting of1-C30A straight-chain or branched hydrocarbon group of (C)6-C30Substituted or unsubstituted benzene rings, or polycyclic aromatic hydrocarbons; or R1、R2Linked through other groups to form cyclic compounds;
or,
when R is7、R8While being H, R5、R6Are each independently selected from C5-C30A nitrogen-containing heterocycle, a substituted nitrogen heterocycle or a fused nitrogen-containing heterocyclic aromatic hydrocarbon of
R1、R2Each independently selected from the group consisting of1-C30A straight-chain or branched hydrocarbon group of (C)6-C30Substituted or unsubstituted benzene rings, or polycyclic aromatic hydrocarbons; or R1、R2By attachment of other groupsA cyclic compound.
The R is1、R2Independently of one another, methyl, ethyl, n-propyl, isopropyl, tert-butyl, - (CH)2)n-and n is not less than 3, phenyl, substituted phenyl, naphthyl, substituted naphthyl, phenanthryl, anthracyl, 9-substituted anthracyl, pyrenyl, fluorenyl or substituted fluorenyl.
The R is1、R2Directly linked to form a cyclic compound, or via-CH2CH2CH2CH2-or 2, 2' -biphenyl to form a cyclic compound.
The derivative has a structure shown in a formula (2) or a formula (3):
further R5、R6、R7、R8Independently of one another, is pyridyl, substituted pyridyl, pyridylphenyl, imidazole, substituted imidazole, thiazole, substituted thiazole, oxazole, substituted oxazole, quinolyl or isoquinolyl.
More preferably, R5And R6Same as R7And R8The same is true.
The 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative is selected from the following structural formula:
the invention also provides an intermediate for preparing the 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative, wherein the intermediate has a structure shown in a formula (4) or a formula (5):
wherein R is1、R2Each independently selected from the group consisting of1-C30A straight-chain or branched hydrocarbon group of (C)6-C30Substituted or unsubstituted benzene rings, or polycyclic aromatic hydrocarbons; or R1、R2Linked through other groups to form cyclic compounds.
The intermediate is a structure shown in formula (A), formula (B), formula (C) or formula (D):
the invention also provides a method for preparing the intermediate A, which comprises the following steps:
(1) carrying out nitration reaction on 10, 10-dimethyl anthrone shown in formula A-I and nitric acid to obtain a disubstituted nitro compound shown in formula A-II;
(2) carrying out Corey-Fuchs dibromoalkylation reaction on a compound shown in a formula A-II and carbon tetrabromide in the presence of triphenylphosphine to obtain a 1, 1-dibromoolefin compound shown in a formula A-III;
(3) under the protection of nitrogen, a compound shown as a formula A-III and trimethylsilyl acetylene are added in PdCl2(PPh3)2In the presence of CuI, carrying out Sonogashira reaction, and then carrying out catalytic removal of trimethylsilyl to obtain a diyne compound shown in formulas A-IV;
(4) dissolving the compounds shown in the formulas A to IV in dry toluene under the protection of nitrogen, and adding PtCl2Carrying out a ring closure reaction to obtain a compound shown as a formula A-V;
(5) dissolving a compound shown in a formula A-V in a mixed solvent of ethanol and THF, carrying out catalytic hydrogenation in the presence of Pd/C to reduce nitro groups into amino groups, and then carrying out diazotization-bromination reaction to obtain an intermediate shown in a formula (A);
the invention also provides a method for preparing the intermediate B, which comprises the following steps:
(1) performing dialkyl cyclization reaction on anthrone and 1, 4-diiodobutane under the condition that potassium tert-butoxide is used as alkali to obtain a compound shown as a formula B-I;
(2) carrying out nitration reaction on the disubstituted anthrone derivative shown in the formula B-I and nitric acid in the presence of concentrated sulfuric acid to obtain a disubstituted nitro compound shown in the formula B-II;
(3) carrying out Corey-Fuchs dibromoalkylation reaction on a compound shown as a formula B-II and carbon tetrabromide in the presence of triphenylphosphine to obtain a 1, 1-dibromoolefin compound shown as a formula B-III;
(4) under the protection of nitrogen, a compound shown as a formula B-III and trimethylsilyl acetylene are added in PdCl2(PPh3)2In the presence of CuI, carrying out Sonogashira reaction, and then carrying out catalytic removal of trimethylsilyl to obtain a diyne compound shown in a formula B-IV;
(5) under the protection of nitrogen, dissolving the compounds shown as the formulas B to IV in dry toluene, and adding PtCl2Carrying out a ring closure reaction to obtain a compound shown as a formula B-V;
(6) dissolving a compound shown as a formula B-V in a mixed solvent of ethanol and THF, carrying out catalytic hydrogenation in the presence of Pd/C to reduce nitro groups into amino groups, and then carrying out diazotization-bromination reaction to obtain an intermediate shown as a formula (B);
the invention also provides a method for preparing the intermediate C, which comprises the following steps:
(1) carrying out Corey-Fuchs dibromoene reaction on dimethyl anthrone and carbon tetrabromide shown in a formula C-I in the presence of triphenylphosphine to obtain a 1, 1-dibromo olefin compound shown in a formula C-II;
(2) by Pd (PPh)3)4Carrying out catalytic cross-coupling reaction on the C-II and a Reformask reagent to obtain a diester compound shown by C-III;
(3) carrying out alkaline hydrolysis and acyl chlorination on the compound shown in the formula C-III to obtain a compound shown in the formula C-IV;
(4) the compound shown in the formula C-IV is processed by AlCl3The bisphenol compound shown in the formula C-V is prepared by catalytic ring closure reaction;
(5) subjecting a compound represented by formula C-V to Br2-PPh3Reacting with a reagent to obtain an intermediate shown as a formula (C);
the invention also provides a method for preparing the intermediate D, which comprises the following steps:
(1) anthracenone and 1, 4-diiodobutane are subjected to dialkyl cyclization reaction under the condition that potassium tert-butoxide is used as alkali to obtain a compound shown as a formula D-I;
(2) carrying out Corey-Fuchs dibromoalkylation reaction on a compound shown in the formula D-I and carbon tetrabromide in the presence of triphenylphosphine to obtain a 1, 1-dibromoolefin compound shown in the formula D-II;
(3) by Pd (PPh)3)4Carrying out catalytic cross-coupling reaction on the D-II and a Reformask reagent to obtain a diester compound shown by D-III;
(4) carrying out alkaline hydrolysis and acyl chlorination on the compound shown in the formula D-III to obtain a compound shown in a formula D-IV;
(5) the compound shown in the formula D-IV is processed by AlCl3A bisphenol compound shown in a formula D-V is prepared by catalytic ring closure reaction;
(6) subjecting a compound represented by formula D-V to Br2-PPh3Reacting with a reagent to obtain an intermediate shown as a formula (D);
the invention also provides a method for preparing the 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative, which is to perform coupling reaction on the intermediate under the protection of nitrogen.
The invention also provides a main material of a light-emitting layer of the organic electroluminescent device, wherein the main material is the 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative.
The invention also provides an organic electroluminescent device, which comprises a substrate, and an anode layer, a plurality of light-emitting unit layers and a cathode layer which are sequentially formed on the substrate;
the luminescent unit layer comprises a hole transport layer, an organic luminescent layer and an electron transport layer, and the main material of the luminescent layer is one or more of the 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivatives.
The luminescent layer comprises a red phosphorescent luminescent layer, and the main material of the red phosphorescent luminescent layer is one or more of 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivatives.
The invention also provides application of the 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative in an organic electroluminescent device.
Compared with the prior art, the compound has the following advantages:
(1) in the present invention, we propose novel 2, 10-and 3, 9-disubstituted 6, 6-disubstituted-6-hbenzo [ cd ] pyrene derivatives having electron-deficient nitrogen-containing heterocycles such as pyridyl, thiazolyl, oxazolyl, imidazolyl or quinolyl, isoquinolyl groups in the molecule, which have excellent electron transport ability, and which can further adjust high thermal and chemical stability which is already excellent by adjusting various substituent groups.
(2) The novel material can be used as an electron transport material in a high-efficiency OLED device and can also be used as a fluorescent or red phosphorescent host material.
Drawings
FIG. 1 shows an embodiment of the present invention1 nuclear magnetic spectrum of compound A: (1H）；
FIG. 2 shows the nuclear magnetic spectrum of compound B in example 2 of the present invention: (1H）；
FIG. 3 is a nuclear magnetic spectrum of Compound C in example 3 of the present invention: (1H）；
FIG. 4 is a nuclear magnetic spectrum of Compound D of example 4 of the present invention: (1H）；
FIG. 5 is the nuclear magnetic spectrum (TM 1) of compound in example 5 of the present invention1H）；
FIG. 6 is the nuclear magnetic spectrum of compound TM4 in example 8 of the present invention: (1H）；
FIG. 7 is the nuclear magnetic spectrum of compound TM5 in example 9 of the present invention: (1H）；
FIG. 8 is the nuclear magnetic spectrum of compound TM12 in example 16 of the present invention: (1H）；
FIG. 9 shows the NMR spectrum of compound TM14 in example 18 of the present invention (1H）；
FIG. 10 is the nuclear magnetic spectrum of compound TM19 in example 23 of the present invention: (1H）；
FIG. 11 is the nuclear magnetic spectrum of compound TM24 in example 28 of the present invention: (1H）；
FIG. 12 is the nuclear magnetic spectrum of compound TM27 in example 31 of the present invention: (1H）；
FIG. 13 is the nuclear magnetic spectrum of compound TM30 in example 34 of the present invention: (1H）；
FIG. 14 is the nuclear magnetic spectrum of compound TM33 in example 37 of the present invention: (1H）；
FIG. 15 is the nuclear magnetic spectrum of compound TM38 in example 42 of the present invention: (1H）；
FIG. 16 is a graph showing the neutralization according to example 46 of the present inventionNuclear magnetic spectrum of compound TM42 (TM 42)1H）；
FIG. 17 is the nuclear magnetic spectrum of compound TM43 in example 47 of the present invention (1H）；
FIG. 18 is the nuclear magnetic spectrum of compound TM45 in example 49 of the present invention: (1H）；
FIG. 19 is the nuclear magnetic spectrum of compound TM48 in example 52 of the present invention: (1H）；
FIG. 20 is the nuclear magnetic spectrum of compound TM49 in example 53 of the present invention: (1H）；
FIG. 21 is the nuclear magnetic spectrum of compound TM52 in example 56 of the present invention: (1H）；
FIG. 22 is the nuclear magnetic spectrum of compound TM53 in example 57 of the present invention: (1H）；
FIG. 23 is the nuclear magnetic spectrum of compound TM54 in example 58 of the present invention: (1H）。
Detailed Description
Nitric acid, sulfuric acid, carbon tetrabromide, triphenylphosphine, trimethylsilyl acetylene, cuprous iodide, bis (triphenylphosphine) palladium dichloride, tetrabutylammonium fluoride, platinum dichloride, 10% palladium/carbon, sodium nitrite, cuprous bromide, 48% hydrobromic acid, zinc powder, ethyl bromoacetate, tetrakis (triphenylphosphine) palladium, lithium hydroxide, thionyl chloride, aluminum trichloride, liquid bromine, 1, 4-diiodobutane, anthrone, potassium tert-butoxide, carbazole and other chemical products are purchased from the domestic chemical product market, 9, 9-dimethylanthrone is synthesized according to literature methods (J.Am.Chem.Soc.1975, 97,6790), and boric acid used in the last coupling reaction can be purchased or prepared according to literature methods (D.J.Hall, boric Acids: Preparation and Applications in organic Synthesis and Medicine, Wiley-Vch, 2005).
Examples 1 to 4 are preparation examples of intermediates of the present invention:
example 1
This example prepares an intermediate 3, 9-dibromo-6, 6-dimethyl-6-H-benzo [ cd ] pyrene of formula (A):
the synthetic route is as follows:
the preparation method comprises the following steps:
(1) synthesis of A-II
150mL of fuming nitric acid was added to a 500mL three-necked flask, cooled to about 5 ℃ with an ice-water bath, and 22.2g of 10, 10-dimethylanthrone A-I (0.1mol) was added in portions with stirring at a rate such that the temperature of the reaction mixture was not higher than 10 ℃ and, after the addition of the reactants was completed, the temperature of the reaction mixture was maintained at 5 ℃ for about 30 min. The reaction was poured into 400mL of ice water, stirred vigorously, and then filtered with suction. Washing the filter cake with water, drying, and recrystallizing with ethanol-petroleum ether mixed solvent to obtain 25g of light yellow solid A-II with yield of 80%;
(2) synthesis of A-III
Corey-Fuchs dibromoalkylation reaction: in a 500mL dry pressure resistant reactor, 25g of A-II (80 mmol), 53g of carbon tetrabromide (160 mmol) were added, and after three evacuation-nitrogen cycles of the reaction system, 250mL of dry benzene were added, the mixture was stirred for 5min, and 83.7g of triphenylphosphine (320 mmol) was added. The reaction mixture is stirred vigorously at 150 ℃ for 48h, the temperature of the system is reduced to room temperature, and sufficient CH is added2Cl2The reaction mixture was dissolved. The crude product is separated by column chromatography (pure)Petroleum ether) to yield 22.5g of pale yellow solid a-III with a yield of 60%;
(3) synthesis of A-IV
Under nitrogen protection, a 250mL pressure-resistant reaction flask was charged with 100mL of a triethylamine solution containing 5.7mL of trimethylsilylacetylene (40 mmol), and 4.7g of dibromo-compound A-III (10mmol) and 0.7g of PdCl were added2(PPh3)2(1 mmol) and 0.38g of CuI (2 mmol), the reaction mixture is heated to 100 ℃ and reacted at this temperature for 20 h. After the system was cooled to room temperature, 100mL of CH was added2Cl2Then washing twice with saturated ammonium chloride solution and water, and drying. The crude product was separated by column chromatography to give 3.77g of a light brown solid in 75% yield;
the light brown solid was dissolved in 30mL CH2Cl215mL of CH containing 10g of tetrabutylammonium fluoride trihydrate were slowly added dropwise2Cl2After the addition of the solution was completed, the reaction was stirred at room temperature for about 1 hour, and the completion of the reaction was checked by TLC. Filtering the reaction solution through a silica gel short column, and draining the solvent to obtain 2.7g of white solids A-IV with the yield close to 100%;
(4) synthesis of A-V
2.7g (7.5 mmol) of the compounds A to IV are dissolved in 50mL of dry toluene under nitrogen, 0.1g of PtCl is added2(0.38m mol,5% eq.). Carrying out reflux reaction for 6h, wherein the reaction solution has no precipitate, and decoloring by using a short silica gel column to obtain 1.35g of orange solid compounds A-V with the yield of 50%;
(5) synthesis of intermediate 3, 9-dibromo-6, 6-dimethyl-6-H benzo [ cd ] pyrene shown as formula A
Dissolving 1.35g A-V in 10mL of a 1:1 mixed solvent of ethanol and THF, adding 1g of 10% Pd/C, vacuumizing and replacing hydrogen to enable the system to form a hydrogen atmosphere, maintaining the system to be under positive hydrogen pressure through a hydrogen balloon, stirring the mixture at room temperature for reaction for 10 hours, removing the raw materials, filtering to remove the palladium-carbon catalyst, and draining the filtrate to obtain 1.3g of light yellow solid with the yield of 95%;
2.98g (10mmol) of the pale yellow solid was dissolved in 15mL of 48% hydrobromic acid, the reaction was cooled to 5 ℃ or lower in an ice-water bath, and 10mL of a solution containing 2.1g of NaNO was slowly dropped2(30 mmol) of the aqueous solution, keeping the temperature of the system not higher than 10 ℃ in the dropping process, and continuing stirring at 5 ℃ for 0.5h after the dropping is finished. Then 5g of CuBr-48% HBr (10 mL) solution was added and the system was heated to 80 ℃ and stirred at this temperature for 3h using CH2Cl2The resulting product was extracted, separated, dried and column chromatographed to yield 3.2g of a white solid, A, in 75% yield.
The mass spectrometric data and the elemental analysis data of the obtained compound A are shown in Table 1, and the nuclear magnetic detection spectrogram of the compound A (1H) See figure 1 for details.
Example 2
This example prepares the intermediate 3, 9-dibromo-6, 6-cyclobutyl-6-H-benzo [ cd ] pyrene of formula B:
the synthetic route is as follows:
the preparation method comprises the following steps:
(1) synthesis of B-I
In a 250mL three-necked flask, 19.4g of anthrone (0.1mol), 150mL of dry THF, 34.1g of 1, 4-diiodobutane (0.11 mol) and 26.8g of potassium tert-butoxide (0.24 mol) were added under stirring, and the reaction was stirred at room temperature for 3 hours and then refluxed for 3 hours. Adding saturated ammonium chloride solution to quench reaction, extracting with ethyl acetate, separating liquid, drying, and separating by column chromatography to obtain 13.6g white solid B-I with yield of 55%;
(2) synthesis of B-II
This step was substantially the same as the step (1) in example 1, except that B-I was used as a starting material (charged amount: 24.6g (0.1 mol)), and that B-II was obtained as a pale yellow solid in an amount of 26.4g with a yield of 78%;
(3) synthesis of B-III
This step was substantially the same as the step (2) in example 1, except that B-II was used as the starting material (addition amount was 27g (80 mmol)), giving 31.9g (yield 65%) of B-III as a pale yellow solid;
(4) synthesis of B-IV
This step was substantially the same as the step (3) in example 1, except that the amount of the dibromo compound B-III added was 4.8g (10mmol), the amount of the finally obtained white solid B-IV was 2.4g, and the total yield of the two steps was about 67%;
(5) synthesis of B-V
This step was substantially the same as the step (4) in example 1 except that the amount of the compounds B to IV added was 2.4g (6.7 mmol), and 1.2g of the resulting orange solid compounds B to V were obtained in a yield of 50%;
(6) synthesis of intermediate (B)
This step was substantially the same as step (5) in example 1, except that the amount of B-V added was 1.2g, the pale yellow solid obtained was 1.15g, and the yield was 94%; the pale yellow solid was added in an amount of 3.24g (10mmol) during the synthesis of intermediate (B) to give 3.5g of white solid B in a yield of 78%. The mass spectrometric data and the elemental analysis data of the compound B are shown in Table 1, and the nuclear magnetic spectrum of the compound B is shown (1H) See figure 2 for details.
Example 3
This example prepares the intermediate 2, 10-dibromo-6, 6-dimethyl-6-hbenzo [ cd ] pyrene of formula C:
the synthetic route is as follows:
the preparation method comprises the following steps:
(1) synthesis of C-II
This step was substantially identical to step (2) in example 1, except that 22.2g (80 mmol) of dimethylanthrone C-I was added to give 24.5g of white solid C-II in 65% yield;
(2) preparation of C-III
N2To a 250mL three-necked flask, 2.6g of zinc dust (0.04mol), a small amount of iodine, and 100mL of dry DMF were added under protection, and stirred until the red color disappeared, 5g of ethyl bromoacetate (30 mmol) was added, heated to 60 deg.C, stirred for 3h, and the resulting solution was filtered into another dry 250mL three-necked flask. 3.78g of the thus-obtained C-II (10mmol) and 0.55g of Pd (PPh) were added3)4(0.5mmol,5% eq.), heated to 120 ℃ and the reaction stirred at this temperature for 15 h. Adding saturated ammonium chloride solution to quench reaction, extracting with ethyl acetate, separating, drying, and separating by column chromatography to obtain 2g of white solid C-III with yield of 55%;
(3) preparation of C-IV
36.4g C-III (0.1mol) was dissolved in 100mL THF, 100mL aqueous solution containing 12g LiOH (0.5 mol) was added, and the mixture was stirred at room temperature until the system became a homogeneous clear solution. The volume of the reaction solution was concentrated under reduced pressure to about 50mL, and the reaction solution was cooled. Adjusting pH to 1 with dilute hydrochloric acid in ice bath, precipitating a large amount of white solid, filtering, washing with water, and drying to obtain 32g of white solid with yield of 97%;
32g of the above white solid was dissolved in 100mL of dichloromethane, and 40mL of SOCl was added2And heating and refluxing for 3 h. Removing the solvent and unreacted thionyl chloride under reduced pressure to obtain a light yellow liquid C-IV;
(4) preparation of C-V
37.3g C-IV (0.1mol) was dissolved in 200mL CCl4In the process, the reaction system is cooled to 0 ℃ and then 40g of freshly sublimed pulverulent AlCl are slowly added3(0.3mol), controlling the reaction temperature to be not higher than 10 ℃, and continuing to react for 30min after the addition is finished. Pouring the reaction mixture into ice water, extracting a product with ethyl acetate, separating liquid, drying, draining the solvent to obtain a crude product, purifying the crude product by an alkali-adjusting acidification method, and then recrystallizing the crude product with ethanol to obtain a white solid C-V25g with the yield of 83%;
(5) preparation of intermediate 2, 10-dibromo-6, 6-dimethyl-6-H benzo [ cd ] pyrene (C)
In a 250mL three-necked flask equipped with a mechanical stirrer, triphenylphosphine and dry acetonitrile were added, liquid bromine was slowly added dropwise under an ice-water bath, and the reaction temperature was controlled to be lower than 40 ℃. After the bromine addition, the bath was changed to an oil bath, 50mL of acetonitrile solution containing 30g C-V (0.1mol) was added dropwise, after the addition, the reaction system was reacted at 60-70 ℃ for 30min, and then the distillation apparatus was changed to evaporate acetonitrile. The reaction was then heated to about 300 ℃ with a hot plate and held at that temperature until HBr evolution ceased. Cooling the system, adding petroleum ether to make the product into fine precipitate, filtering, and washing with petroleum ether. The filtrate was washed with NaOH solution, dried, and separated by column chromatography for 21g to obtain white solid C with a yield of 50%. The mass spectrometric data and the elemental analysis data of the compound C are shown in Table 1, and the nuclear magnetic spectrum of the compound C is shown (1H) See figure 3 for details.
Example 4
This example prepares an intermediate of formula D:
the synthetic route is as follows:
the preparation method comprises the following steps:
(1) synthesis of D-I
This step was substantially the same as the procedure in step (1) of example 2 to give a compound represented by formula D-I;
(2) preparation of D-II
This step was substantially the same as step (1) in example 3, except that D-I was used in an amount of 24.8g (80 mmol) to give 20g of D-II as a white solid in a yield of 50%;
(23) preparation of D-III
This step was substantially the same as step (2) in example 3, except that D-II was used in an amount of 4g (10mmol), and D-III was obtained as a white solid in an amount of 1.95g with a yield of 50%;
(4) preparation of D-IV
This step was substantially the same as step (3) in example 3, except that D-III was used in an amount of 39g (0.1mol) to give 35g of D-IV as a white solid in a yield of 97%;
(5) preparation of D-V
This step was substantially the same as step (4) in example 3, except that D-IV was used in an amount of 40g (0.1mol), and that D-V was obtained as a white solid in an amount of 26g with a yield of 80%;
(6) preparation of intermediate D
This step substantially coincides with step (5) in example 3,except that D-V was used in an amount of 32.6g (0.1mol) and that 27g of D was obtained as a white solid in a yield of 60%. The mass spectrometric data and the elemental analysis data of the compound D are shown in Table 1, and the nuclear magnetic spectrum of the compound D is shown (1H) See figure 4 for details.
Example 5-example 56 are examples of the preparation of title compounds of the present invention using intermediate A, B, C or D:
example 5
This example prepares compound TM1, which has the structure shown below:
the synthetic route is as follows:
the preparation method comprises the following steps:
under the protection of nitrogen, 4.3g of 3, 9-dibromo-6, 6-dimethyl-6-H-benzo [ cd ] shown in the formula A]Pyrene (10mmol), 3.08g 2-pyridineboronic acid (25mmol) and 30mL toluene were added to a 250mL three-necked reaction flask, followed by 20mL ethanol, 30mL saturated Na2CO3Solution and 232mgPd (PPh)3)4(0.2mmol, 2% eq.), stirring, heating to reflux, monitoring the reaction by TLC until completion, stopping the reaction, filtering while hot, washing with 50mL of dichloromethane, evaporating the solvent under reduced pressure to obtain a crude product, and performing column chromatography with a petroleum ether/dichloromethane system to obtain 2.7g of a white solid TM1 with a yield of 65%.
The mass spectrometric data and the elemental analysis data of the compound TM1 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM1 is shown (1H) For details seeFigure 5 is a drawing.
Example 6
This example prepares compound TM2, which has the structure shown below:
the synthetic route is as follows:
the preparation method comprises the following steps:
under the protection of nitrogen, 4.3g of intermediate 2, 10-dibromo-6, 6-dimethyl-6-H-benzo [ cd ]]Pyrene (C) (10mmol), 3.08g 2-pyridineboronic acid (25mmol) and 30mL toluene were added to a 250mL three-necked reaction flask, followed by 20mL ethanol, 30mL saturated Na2CO3Solution and 232mgPd (PPh)3)4(0.2mmol, 2% eq.), stirring, heating to reflux, monitoring the reaction by TLC, stopping the reaction after the reaction is completed, filtering while hot, washing with 50mL of dichloromethane, evaporating the solvent under reduced pressure, and performing column chromatography on the obtained crude product by a petroleum ether/dichloromethane system to obtain 3.0g of white solid TM2 with the yield of 70%. The mass spectrometric data and the elemental analysis data of compound TM2 obtained are detailed in table 1.
Example 7
This example prepares compound TM3, which has the structure shown below:
the synthetic route is as follows:
the preparation method comprises the following steps:
intermediate B (10mmol), 3.08g 2-pyridineboronic acid (25mmol) and 30mL toluene were added to a 250mL three-necked flask under nitrogen, followed by 20mL ethanol, 30mL saturated Na2CO3Solution and 232mg Pd (PPh)3)4(0.2mmol, 2% eq.), stirring, heating to reflux, monitoring the reaction by TLC, stopping the reaction after the reaction is completed, filtering while hot, washing with 50mL of dichloromethane, evaporating the solvent under reduced pressure, and performing column chromatography on the obtained crude product by a petroleum ether/dichloromethane system to obtain 3.4g of white solid TM3 with the yield of 76%. The mass spectrometric data and the elemental analysis data of compound TM3 obtained are detailed in table 1.
Example 8
This example prepares compound TM4, which has the structure shown below:
the synthetic route is as follows:
the preparation method comprises the following steps:
4.5g of intermediate D (10mmol), 3.08g of 2-pyridineboronic acid (25mmol) and 30mL of toluene were added to a 250mL three-necked reaction flask under nitrogen, followed by 20mL of ethanol, 30mL of saturated Na2CO3Solution and 232mg Pd (PPh)3)4(0.2mmol, 2% eq.), stirring, heating to reflux, monitoring the reaction by TLC until the reaction is complete, stopping the reaction, filtering while hot, and repeatingThe crude product was purified by washing with 50mL of methylene chloride and removing the solvent by evaporation under reduced pressure, and column chromatography of the crude product was carried out using a petroleum ether/methylene chloride system to give 3.2g of TM4 as a white solid in 71% yield.
The mass spectrometric data and the elemental analysis data of the compound TM4 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM4 is shown (1H) See figure 6 for details.
Example 9
This example prepares compound TM5, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 3-pyridineboronic acid, the other starting materials and procedures were the same as in example 5, and TM5 was obtained as a white solid in a yield of 2.7g and 63%.
The mass spectrometric data and the elemental analysis data of the compound TM5 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM5 is shown (1H) See figure 7 for details.
Example 10
This example prepares compound TM6, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 3-pyridineboronic acid, and the other starting materials and procedures were the same as in example 6, to give 3.0g of TM6 as a white solid in 72% yield. The mass spectrometric data and the elemental analysis data of compound TM6 obtained are detailed in table 1.
Example 11
This example prepares compound TM7, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 3-pyridineboronic acid, and the other starting materials and procedures were the same as in example 7, to give 3.1g of TM7 as a white solid in 70% yield. The mass spectrometric data and the elemental analysis data of compound TM7 obtained are detailed in table 1.
Example 12
This example prepares compound TM8, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 3-pyridineboronic acid, and the other starting materials and procedures were the same as in example 8, to give 2.96g of TM8 as a white solid in 66% yield. The mass spectrometric data and the elemental analysis data of compound TM8 obtained are detailed in table 1.
Example 13
This example prepares compound TM9, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 4-pyridineboronic acid, and the other starting materials and procedures were the same as in example 5, to give 2.96g of TM9 as a white solid in 70% yield. The mass spectrometric data and the elemental analysis data of compound TM9 obtained are detailed in table 1.
Example 14
This example prepares compound TM10, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 4-pyridineboronic acid, and the other starting materials and procedures were the same as in example 6, to give 2.7g of TM10 as a white solid in 64% yield. The mass spectrometric data and the elemental analysis data of compound TM10 obtained are detailed in table 1.
Example 15
This example prepares compound TM11, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 4-pyridineboronic acid, and the other starting materials and procedures were the same as in example 7, to give 3.18g of TM11 as a white solid in 71% yield. The mass spectrometric data and the elemental analysis data of compound TM11 obtained are detailed in table 1.
Example 16
This example prepares compound TM12, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 4-pyridineboronic acid, and the other starting materials and procedures were the same as in example 8, to give 3.14g of TM12 as a white solid in a yield of 70%.
The mass spectrometric data and the elemental analysis data of the compound TM12 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM12 is shown (1H) See figure 8 for details.
Example 17
This example prepares compound TM13, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 5-phenyl-2-pyridineboronic acid, and the other raw materials and procedures were the same as in example 5 to obtain 4.0g of TM13 as a white solid with a yield of 70%. The mass spectrometric data and the elemental analysis data of compound TM13 obtained are detailed in table 1.
Example 18 this example prepares compound TM14, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 5-phenyl-2-pyridineboronic acid, and the other raw materials and procedures were the same as in example 6 to give 4.77g of TM14 as a white solid in 83% yield.
The mass spectrometric data and the elemental analysis data of the compound TM14 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM14 is shown (1H) See figure 9 for details.
Example 19 this example prepares compound TM15, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 5-phenyl-2-pyridineboronic acid, and the other raw materials and procedures were the same as in example 7 to give 4.9g of TM15 as a white solid in 83% yield. The mass spectrometric data and the elemental analysis data of compound TM15 obtained are detailed in table 1.
Example 20 this example prepared compound TM16, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 5-phenyl-2-pyridineboronic acid, and the other raw materials and procedures were the same as in example 8 to give 4.2g of TM16 as a white solid in 70% yield. The mass spectrometric data and the elemental analysis data of compound TM16 obtained are detailed in table 1.
Example 21 this example prepares compound TM17, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 6-phenyl-3-pyridineboronic acid, and the other starting materials and procedures were the same as in example 5 to give 4.5g of TM17 as a white solid in 78% yield. The mass spectrometric data and the elemental analysis data of compound TM17 obtained are detailed in table 1.
Example 22 this example prepares compound TM18, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 6-phenyl-3-pyridineboronic acid, and the other starting materials and procedures were the same as in example 6 to give 3.96g of TM18 as a white solid in 69% yield. The mass spectrometric data and the elemental analysis data of compound TM18 obtained are detailed in table 1.
Example 23 this example prepares compound TM19, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 6-phenyl-3-pyridineboronic acid, and the other starting materials and procedures were the same as in example 7 to give 4.9g of TM19 as a white solid in 81% yield.
The mass spectrometric data and the elemental analysis data of the compound TM19 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM19 is shown (1H) See figure 10 for details.
Example 24 this example prepares compound TM20, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 6-phenyl-3 pyridineboronic acid, and the other starting materials and procedures were the same as in example 8 to give 4.3g of TM20 as a white solid in 72% yield. The mass spectrometric data and the elemental analysis data of compound TM20 obtained are detailed in table 1.
Example 25 this example prepares compound TM21, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 4- (2-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 5 to give 3.8g of TM21 as a white solid in 65% yield. The mass spectrometric data and the elemental analysis data of compound TM21 obtained are detailed in table 1.
Example 26 this example prepares compound TM22, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 4- (2-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 6 to give 3.7g of TM22 as a white solid in 64% yield. The mass spectrometric data and the elemental analysis data of compound TM22 obtained are detailed in table 1.
Example 27 this example prepared compound TM23, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 4- (2-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 7 to give 3.7g of TM23 as a white solid in 62% yield. The mass spectrometric data and the elemental analysis data of compound TM23 obtained are detailed in table 1.
Example 28 this example prepared compound TM24, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 4- (2-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 8 to give 3.4g of TM24 as a white solid in 59% yield.
The mass spectrometric data and the elemental analysis data of the compound TM24 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM24 is shown (1H) See figure 11 for details.
Example 29 this example prepares compound TM25, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 4- (3-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 5 to give 3.54g of TM25 as a white solid in 65% yield. The mass spectrometric data and the elemental analysis data of compound TM25 obtained are detailed in table 1.
Example 30 this example prepares compound TM26, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 4- (3-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 6 to give 3.85g of TM26 as a white solid in 64% yield. The mass spectrometric data and the elemental analysis data of compound TM26 obtained are detailed in table 1.
Example 31 this example prepared compound TM27, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 4- (3-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 7 to give 3.6g of TM27 as a white solid in 62% yield.
The mass spectrometric data and the elemental analysis data of the compound TM27 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM27 is shown (1H) See figure 12 for details.
Example 32 this example prepares compound TM28, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 4- (3-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 8 to give 3.6g of TM28 as a white solid in 59% yield. The mass spectrometric data and the elemental analysis data of compound TM28 obtained are detailed in table 1.
Example 33 this example prepared compound TM29, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 4- (4-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 5 to give 3.4g of TM29 as a white solid in 65% yield. The mass spectrometric data and the elemental analysis data of compound TM29 obtained are detailed in table 1.
Example 34 this example prepares compound TM30, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 4- (4-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 6 to give 3.2g of TM30 as a white solid in 55% yield.
The mass spectrometric data and the elemental analysis data of the compound TM30 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM30 is shown (1H) See figure 13 for details.
Example 35 this example prepared compound TM31, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 4- (4-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 7 to give 3.1g of TM31 as a white solid in 52% yield. The mass spectrometric data and the elemental analysis data of compound TM31 obtained are detailed in table 1.
Example 36 this example prepares compound TM32, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 4- (4-pyridyl) phenylboronic acid, and the other raw materials and procedures were the same as in example 8 to give 3g of TM32 as a white solid in 50% yield. The mass spectrometric data and the elemental analysis data of compound TM32 obtained are detailed in table 1.
Example 37 this example prepares compound TM33, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 2-quinolineboronic acid and the other starting materials and procedures were the same as in example 5 to give 2.7g of TM33 as a white solid in 57% yield.
The mass spectrometric data and the elemental analysis data of the compound TM33 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM33 is shown (1H) See figure 14 for details.
Example 38 this example prepares compound TM34, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 2-quinolineboronic acid and the other starting materials and procedures were the same as in example 6 to give 2.6g of TM34 as a white solid in 50% yield. The mass spectrometric data and the elemental analysis data of compound TM34 obtained are detailed in table 1.
Example 39 this example prepares compound TM35, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 2-quinolineboronic acid and the other starting materials and procedures were the same as in example 7 to give 3.7g of TM35 as a white solid in 65% yield. The mass spectrometric data and the elemental analysis data of compound TM35 obtained are detailed in table 1.
Example 40 this example prepared compound TM36, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 2-quinolineboronic acid and the other starting materials and procedures were the same as in example 8 to give 3.66g of TM36 as a white solid in 66% yield. The mass spectrometric data and the elemental analysis data of compound TM36 obtained are detailed in table 1.
Example 41 this example prepares compound TM37, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 1-isoquinolineboronic acid and the other starting materials and procedures were the same as in example 5 to give 3.5g of TM37 as a white solid in 65% yield. The mass spectrometric data and the elemental analysis data of compound TM37 obtained are detailed in table 1.
Example 42 this example prepares compound TM38, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 1-isoquinolineboronic acid and the other starting materials and procedures were the same as in example 6 to give 3.2g of TM38 as a white solid in 58% yield.
The mass spectrometric data and the elemental analysis data of the compound TM38 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM38 is shown (1H) See figure 15 for details.
Example 43 this example prepares compound TM39, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 1-isoquinolineboronic acid and the other starting materials and procedures were the same as in example 7 to give 3.26g of TM39 as a white solid in 60% yield. The mass spectrometric data and the elemental analysis data of compound TM39 obtained are detailed in table 1.
Example 44 this example prepares compound TM40, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 1-isoquinolineboronic acid and the other starting materials and procedures were the same as in example 8 to give 3.73g of TM40 as a white solid in 68% yield. The mass spectrometric data and the elemental analysis data of compound TM40 obtained are detailed in table 1.
Example 45 this example prepares compound TM41, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 4- (2-phenyl-1-1H-benzimidazole) phenylboronic acid and the other starting materials and procedures were identical to those of example 5 to give 5.4g of TM41 as a white solid in 67% yield. The mass spectrometric data and the elemental analysis data of compound TM41 obtained are detailed in table 1.
Example 46 this example prepares compound TM42, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 4- (2-phenyl-1-1H-benzimidazole) phenylboronic acid and the other starting materials and procedures were identical to those of example 6 to give 4.75g of TM42 as a white solid in 59% yield.
The mass spectrometric data and the elemental analysis data of the compound TM42 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM42 is shown (1H) See figure 16 for details.
Example 47 this example prepares compound TM43, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 4- (2-phenyl-1-1H-benzimidazole) phenylboronic acid and the other starting materials and procedures were identical to those of example 7 to give 4.57g of TM43 as a white solid in 55% yield.
The mass spectrometric data and the elemental analysis data of the compound TM43 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM43 is shown (1H) See figure 17 for details.
Example 48 this example prepares compound TM44, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 4- (2-phenyl-1-1H-benzimidazole) phenylboronic acid and the other starting materials and procedures were identical to those of example 8 to give 5.65g of TM44 as a white solid in 68% yield. The mass spectrometric data and the elemental analysis data of compound TM43 obtained are detailed in table 1.
Example 49 this example prepared compound TM45, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of 2-benzothiazoleboronic acid and the other starting materials and procedures were the same as in example 5 to give 3.16g of TM45 as a white solid in 59% yield.
The mass spectrometric data and the elemental analysis data of the compound TM45 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM45 is shown (1H) See figure 18 for details.
Example 50 this example prepares compound TM46, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of 2-benzothiazoleboronic acid and the other starting materials and procedures were the same as in example 6 to give 3.85g of TM46 as a white solid in 72% yield. The mass spectrometric data and the elemental analysis data of compound TM46 obtained are detailed in table 1.
Example 51 this example prepares compound TM47, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of 2-benzothiazoleboronic acid and the other starting materials and procedures were the same as in example 7 to give 3.42g of TM47 as a white solid in 61% yield. The mass spectrometric data and the elemental analysis data of compound TM47 obtained are detailed in table 1.
Example 52 this example prepares compound TM48, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of 2-benzothiazoleboronic acid and the other starting materials and procedures were the same as in example 8 to give 4.2g of TM48 as a white solid in 75% yield.
Mass spectrometric detection data and elemental analysis data of the obtained compound TM48According to the details shown in Table 1, the nuclear magnetic detection spectrum of the compound TM48 (1H) See figure 19 for details.
Example 53 this example prepares compound TM49, which has the structure shown below:
the 2-pyridineboronic acid from example 5 was replaced with an equivalent amount of diphenyloxazole boronic acid and the other starting materials and procedures were the same as in example 5 to give 4.46g of TM49 as a white solid in 63% yield.
The mass spectrometric data and the elemental analysis data of the compound TM49 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM49 is shown (1H) See figure 20 for details.
Example 54 this example prepares compound TM50, which has the structure shown below:
the 2-pyridineboronic acid from example 6 was replaced with an equivalent amount of diphenyloxazole boronic acid and the other starting materials and procedures were the same as in example 6 to give 5.24g of TM50 as a white solid in 74% yield. The mass spectrometric data and the elemental analysis data of compound TM50 obtained are detailed in table 1.
Example 55 this example prepares compound TM51, which has the structure shown below:
the 2-pyridineboronic acid from example 7 was replaced with an equivalent amount of diphenyloxazole boronic acid and the other starting materials and procedures were the same as in example 7 to give 5g of TM51 as a white solid in 68% yield. The mass spectrometric data and the elemental analysis data of compound TM51 obtained are detailed in table 1.
Example 56 this example prepares compound TM52, which has the structure shown below:
the 2-pyridineboronic acid from example 8 was replaced with an equivalent amount of diphenyloxazole boronic acid and the other starting materials and procedures were the same as in example 8 to give 5.51g of TM52 as a white solid in 75% yield.
The mass spectrometric data and the elemental analysis data of the compound TM52 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM52 is shown (1H) See figure 21 for details.
Example 57 this example prepares compound TM53, which has the structure shown below:
the preparation method comprises the following steps:
(1) synthesis of E-II
A500 mL three-necked flask was charged with 26.4g of E-I (prepared according to the method provided by J.org.chem.1992,57, 2917-2921) and 250mL of methylene chloride, dissolved, and then freshly prepared activated manganese dioxide was added, the reaction was monitored by TLC, and the activated manganese dioxide was continuously added until the reaction was complete, filtered to remove manganese dioxide, and the filtrate was concentrated to give 22g of E-II as a white solid by recrystallization from ethanol in a yield of 79%;
(2) synthesis of E-III
150mL of fuming nitric acid was added to a 500mL three-necked flask, and cooled to about 5 ℃ in an ice-water bath, and 27.8g of 10-ethyl-10-n-butylanthranilic acid I (0.1mol) was added in portions with stirring at such a rate that the temperature of the reaction solution became not higher than 10 ℃ and, after completion of the addition of the reactants, the temperature of the reaction solution was maintained at 5 ℃ for about 30 min. The reaction was poured into 400mL of ice water, stirred vigorously, and then filtered with suction. Washing the filter cake with water, drying, and recrystallizing with ethanol-petroleum ether mixed solvent to obtain 27.6g of light yellow solid E-III with yield of 75%;
(3) synthesis of E-IV
Corey-Fuchs dibromoalkylation reaction: into a 500mL dry pressure resistant reactor, 2.95g E-III (80 mmol), 53g carbon tetrabromide (160 mmol) were added, and after three evacuation-nitrogen cycles of the reaction system, 250mL dry benzene was added, the mixture was stirred for 5min, and 83.7g triphenylphosphine (320 mmol) was added. The reaction mixture is stirred vigorously at 150 ℃ for 48h, the temperature of the system is reduced to room temperature, and sufficient CH is added2Cl2The reaction mixture was dissolved. The crude product was isolated by column chromatography (pure petroleum ether) to yield 27.2g of a pale yellow solid E-IV, 65% yield;
(4) synthesis of E-V
Under nitrogen protection, a 250mL pressure-resistant reaction flask was charged with 100mL of a triethylamine solution containing 5.7mL of trimethylsilylacetylene (40 mmol), and 5.2g of a dibromo-compound E-IV (10mmol) and 0.7g of PdCl2(PPh3)2(1 mmol) and 0.38g of CuI (2 mmol), the reaction mixture is heated to 100 ℃ and reacted at this temperature for 20 h. After the system was cooled to room temperature, 100mL of CH was added2Cl2Then washing twice with saturated ammonium chloride solution and water, and drying. The crude product was separated by column chromatography to give 3.9g of a light brown solid in 70% yield;
the light brown solid was dissolved in 30mL CH2Cl215mL of CH containing 10g of tetrabutylammonium fluoride trihydrate were slowly added dropwise2Cl2Solution of, addAfter completion, the reaction was stirred at room temperature for about 1h and checked by TLC for completion. Filtering the reaction solution through a silica gel short column, and draining the solvent to obtain 2.9g of white solid E-V with the yield close to 100%;
(5) synthesis of E-VI
Under nitrogen, 3.1g (7.5 mmol) of the compound E-V are dissolved in 50mL of dry toluene, and 0.1g of PtCl is added2(0.38m mol,5% eq.). Carrying out reflux reaction for 6h, wherein the reaction solution has no precipitate, and decoloring by using a short silica gel column to obtain 1.71g of orange solid compound E-VI with the yield of 55%;
(6) synthesis of intermediate 3, 9-dibromo-6-ethyl-6-n-butyl-6-H benzo [ cd ] pyrene shown as formula E
Dissolving 1.71g E-VI in 10mL of a 1:1 mixed solvent of ethanol and THF, adding 1g of 10% Pd/C, evacuating and replacing hydrogen to form a hydrogen atmosphere, maintaining the system to be under positive hydrogen pressure by a hydrogen balloon, stirring the mixture at room temperature for reaction for 10h, removing the raw materials, filtering to remove the palladium-carbon catalyst, and draining the filtrate to obtain 1.65g of light yellow solid with the yield of 98%;
3.5g (10mmol) of the pale yellow solid was dissolved in 15mL of 48% hydrobromic acid, the reaction was cooled to 5 ℃ or lower in an ice-water bath, and 10mL of a solution containing 2.1g of NaNO was slowly dropped2(30 mmol) of the aqueous solution, keeping the temperature of the system not higher than 10 ℃ in the dropping process, and continuing stirring at 5 ℃ for 0.5h after the dropping is finished. Then 5g of CuBr-48% HBr (10 mL) solution was added and the system was heated to 80 ℃ and stirred at this temperature for 3h using CH2Cl2Extracting the generated product, separating, drying and separating by column chromatography to obtain 3.3g of white solid E with the yield of 69%;
(7) synthesis of TM53
Under nitrogen, 4.82g E (10mmol),3.06g 1-pyridineboronic acid (25mmol) and 30mL toluene were added to a 250mL three-necked reaction flask, followed by 20mL ethanol, 30mL saturated Na2CO3Solution and 232mg Pd (PPh)3)4(0.2mmol, 2% eq.), stirred and warmed to reflux, the reaction was monitored by TLC to completion and stoppedThe reaction is carried out, the hot reaction product is filtered, then dichloromethane 50mL is used for washing, the solvent is removed by reduced pressure evaporation, and the obtained crude product is subjected to column chromatography by a petroleum ether/dichloromethane system to obtain 3.3g of white solid TM53 with the yield of 70%.
The mass spectrometric data and the elemental analysis data of the compound TM53 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM53 is shown (1H) See figure 22 for details.
Example 58 this example prepares compound TM54, which has the structure and synthetic procedure shown below:
the preparation method comprises the following steps:
(1) synthesis of F-II
32.6g of F-I (0.1mol) (prepared according to the method provided by Angew. chem., int. Ed.,48(22), 4009-. Quenching the reaction with saturated ammonium chloride solution, extracting with ethyl acetate for three times, mixing organic phases, drying, and extracting to obtain crude product of solvent, and separating by column chromatography to obtain white solid F-II26.7g with yield of 81%;
(2) synthesis of F-III
Adding 33g of F-II (0.1mol) and 250mL of dichloromethane into a 500mL three-necked bottle, adding freshly prepared active manganese dioxide after dissolving, monitoring the reaction by TLC, continuously supplementing active manganese dioxide until the reaction is complete, filtering to remove manganese dioxide, concentrating the filtrate, and recrystallizing the obtained crude product with ethanol to obtain 29.2g of white solid F-III with the yield of 85%;
(3) synthesis of F-IV
Corey-Fuchs dibromoalkylation reaction: into a 500mL dry pressure resistant reactor, 27.5g F-III (80 mmol), 53g carbon tetrabromide (160 mmol) were added, and after three evacuation-nitrogen cycles of the reaction system, 250mL dry benzene was added, the mixture was stirred for 5min, and 83.7g triphenylphosphine (320 mmol) was added. The reaction mixture is stirred vigorously at 150 ℃ for reaction for 48h, the temperature of the system is reduced to room temperature, and a proper amount of CH is added2Cl2The reaction mixture was dissolved. The crude product was separated by column chromatography (pure petroleum ether) to give 25.2g of F-IV as a pale yellow solid in 63% yield;
(4) synthesis of F-V
N2To a 250mL three-necked flask, 2.6g of zinc dust (0.04mol), a small amount of iodine, and 100mL of dry DMF were added under protection, and stirred until the red color disappeared, 5g of ethyl bromoacetate (30 mmol) was added, heated to 60 deg.C, stirred for 3h, and the resulting solution was filtered into another dry 250mL three-necked flask. 5g F-IV (10mmol) and 0.55g Pd (PPh) were added3)4(0.5mmol,5% eq.), heated to 120 ℃ and the reaction stirred at this temperature for 15 h. Adding saturated ammonium chloride solution to quench reaction, extracting with ethyl acetate, separating, drying, and separating by column chromatography to obtain 3.2g white solid F-V with yield of 62%;
(5) synthesis of F-VI
51g F-V (0.1mol) was dissolved in 100mL THF, 100mL aqueous solution containing 12g LiOH (0.5 mol) was added, and the mixture was stirred at room temperature until the system became a homogeneous clear solution. The volume of the reaction solution was concentrated under reduced pressure to about 50mL, and the reaction solution was cooled. Adjusting pH to 1 with dilute hydrochloric acid in ice bath, precipitating a large amount of white solid, filtering, washing with water, and drying to obtain 44g white solid with yield of 95%;
44g of the above white solid was dissolved in 100mL of dichloromethane, and 40mL of SOCl was added2And heating and refluxing for 3 h. Removing the solvent and unreacted thionyl chloride under reduced pressure to obtain a light yellow liquid F-VI;
(6) preparation of F-VII
49.5g F-VI (0.1mol) was dissolved in 200mL CCl4In the process, the reaction system is cooled to 0 ℃ and then 40g of freshly sublimed pulverulent AlCl are slowly added3(0.3mol), controlling the reaction temperature to be not higher than 10 ℃, and continuing to react for 30min after the addition is finished. Pouring the reaction mixture into ice water, extracting the product with ethyl acetate, separating liquid, drying, draining the solvent to obtain a crude product, purifying the crude product by a base-acidification method, and then recrystallizing the crude product with ethanol to obtain a white solid F-VII33.8g with the yield of 80%.
(7) Preparation of F
In a 250mL three-necked flask equipped with a mechanical stirrer, triphenylphosphine and dry acetonitrile were added, liquid bromine was slowly added dropwise under an ice-water bath, and the reaction temperature was controlled to be lower than 40 ℃. After the addition of bromine, the bath was changed to an oil bath, 50mL of acetonitrile solution containing 42.2g F-VII (0.1mol) was added dropwise, after the addition, the reaction system was reacted at 60-70 ℃ for 30min, and then the distillation apparatus was changed to evaporate acetonitrile. The reaction was then heated to about 300 ℃ with a hot plate and held at that temperature until HBr evolution ceased. Cooling the system, adding petroleum ether to make the product into fine precipitate, filtering, and washing with petroleum ether. Washing the filtrate with NaOH solution, drying, and separating by column chromatography to obtain 27g of white solid F with a yield of 50%;
(8) synthesis of TM54
5.48g F (10mmol), 4.95g 2-phenyl 5-pyridineboronic acid (25mmol) and 30mL toluene were added to a 250mL three-necked reaction flask under nitrogen, followed by 20mL ethanol, 30mL saturated Na2CO3Solution and 232mg Pd (PPh)3)4(0.2mmol, 2% eq.), stirring, heating to reflux, monitoring the reaction by TLC until completion, stopping the reaction, filtering while hot, washing with 50mL of dichloromethane, evaporating the solvent under reduced pressure to obtain a crude product, and performing column chromatography with a petroleum ether/dichloromethane system to obtain 5.56g of a white solid TM54 with a yield of 80%.
The mass spectrometric data and the elemental analysis data of the compound TM54 are shown in Table 1, and the nuclear magnetic spectrum of the compound TM54 is shown (1H) See figure 23 for details.
The mass spectrum and elemental analysis data for the aforementioned compounds of the invention, TM1-TM54, are detailed in Table 1 below:
TABLE 1 Mass Spectrometry and elemental analysis data for Compounds TM1-TM54
Example 59 is an example of the use of the compounds of the present invention
In order to compare the transport performance of the electron transport materials, the invention designs a simple electroluminescent device, and uses EM1 doped TBPe as a luminescent layer (EM 1 is a host material, TBPe is a luminescent material), and uses a material with high electron transport performance Bphen as a comparison.
The structure of the organic electroluminescent device in the embodiment of the invention is as follows:
substrate/anode/Hole Transport Layer (HTL)/organic light Emitting Layer (EL)/Electron Transport Layer (ETL)/cathode.
The substrate may be a substrate used in a conventional organic light emitting device, for example: glass or plastic. In the invention, the glass substrate and the ITO are used as anode materials in the manufacture of the organic electroluminescent device.
Various triarylamine-based materials may be used for the hole transport layer. The hole transport material selected for use in the fabrication of the organic electroluminescent device of the present invention is NPB.
The cathode can adopt a metal and a mixture structure thereof, such as Mg: ag. Ca: ag, etc., or an electron injection layer/metal layer structure, such as LiF/Al, Li2O/Al and the like. The cathode material selected in the preparation of the organic electroluminescent device is LiF/Al.
Example 60
The compound in this embodiment is used as an electron transport material in an organic electroluminescent device, and the EML is used as a light emitting layer material, so that a plurality of organic electroluminescent devices are prepared, and the structure of each organic electroluminescent device is as follows: ITO/NPB (40 nm)/EML (30nm)/ETL material (30 nm)/LiF (0.5 nm)/Al (150 nm);
one of the substrates is compared with an organic electroluminescent device, the electronic transmission material is Bphen, and the other organic electroluminescent devices are made of the material of the invention.
The preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form NPB as a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 40 nm;
vacuum evaporation is carried out on the hole transport layer by adopting a double-source co-evaporation method to obtain a main material EM1 and a doped luminescent material TBPe, wherein the rate ratio of EM1 to TBPe is 100:5, the evaporation rate of EM1 is 0.1nm/s, the evaporation rate of TBPe is 0.005nm/s, and the total evaporation film thickness is 30 nm;
a layer of the compound or Bphen of the invention is vacuum evaporated on the luminescent layer to be used as an electron transport layer of the organic electroluminescent device, the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30 nm;
LiF with the thickness of 0.5nm is evaporated on the Electron Transport Layer (ETL) in vacuum to be used as an electron injection layer, and Al with the thickness of 150nm is used as a cathode.
The organic electroluminescent device properties are given in the following table:
as can be seen from the above table, the organic material of the present invention can be used as an electron transport layer material in an organic electroluminescent device.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (5)

1. A6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative characterized in that,
the derivatives are selected from the following structural formulas:
2. a light-emitting layer host material of an organic electroluminescent device, characterized in that the host material is the 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative of claim 1.
3. An organic electroluminescent device comprises a substrate, and an anode layer, a plurality of light emitting unit layers and a cathode layer which are sequentially formed on the substrate;
the light-emitting unit layer comprises a hole transport layer, an organic light-emitting layer and an electron transport layer, and is characterized in that:
the host material of the light-emitting layer is one or more 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivatives of claim 1.
4. The organic electroluminescent device according to claim 3, wherein:
the light-emitting layer comprises a red phosphorescent light-emitting layer, and the host material of the red phosphorescent light-emitting layer is one or more 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivatives as claimed in claim 1.
5. Use of the 6, 6-disubstituted-6-H-benzo [ cd ] pyrene derivative of claim 1 for organic electroluminescent devices.
CN201310250838.1A 2012-06-21 2013-06-21 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates Active CN103508940B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310250838.1A CN103508940B (en) 2012-06-21 2013-06-21 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN2012102078336 2012-06-21
CN201210207833 2012-06-21
CN201210207833.6 2012-06-21
CN201310250838.1A CN103508940B (en) 2012-06-21 2013-06-21 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates

Publications (2)

Publication Number Publication Date
CN103508940A CN103508940A (en) 2014-01-15
CN103508940B true CN103508940B (en) 2017-05-03

Family

ID=49892425

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310250838.1A Active CN103508940B (en) 2012-06-21 2013-06-21 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates

Country Status (1)

Country Link
CN (1) CN103508940B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3533788A1 (en) * 2018-02-28 2019-09-04 Novaled GmbH Organic material for an electronic optoelectronic device and electronic device comprising the organic material

Families Citing this family (77)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103664906B (en) * 2012-09-26 2016-03-09 昆山维信诺显示技术有限公司 A kind of 6,6-dimethyl-6H-benzo [cd] pyrene derivatives and application thereof
KR101809897B1 (en) * 2014-11-07 2017-12-20 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
CN104649961B (en) * 2015-02-04 2017-09-19 固安鼎材科技有限公司 Luminescent layer material of main part and organic electroluminescence device
CN104628623B (en) * 2015-02-04 2017-03-22 北京鼎材科技有限公司 2,6,6,8-tetra-substituted-6H-benzo[cd]pyrene compound and organic electroluminescence device containing same
US9929361B2 (en) 2015-02-16 2018-03-27 Universal Display Corporation Organic electroluminescent materials and devices
US11056657B2 (en) 2015-02-27 2021-07-06 University Display Corporation Organic electroluminescent materials and devices
US9859510B2 (en) 2015-05-15 2018-01-02 Universal Display Corporation Organic electroluminescent materials and devices
US10418568B2 (en) 2015-06-01 2019-09-17 Universal Display Corporation Organic electroluminescent materials and devices
US11127905B2 (en) 2015-07-29 2021-09-21 Universal Display Corporation Organic electroluminescent materials and devices
US10672996B2 (en) 2015-09-03 2020-06-02 Universal Display Corporation Organic electroluminescent materials and devices
US20170229663A1 (en) 2016-02-09 2017-08-10 Universal Display Corporation Organic electroluminescent materials and devices
US10236456B2 (en) 2016-04-11 2019-03-19 Universal Display Corporation Organic electroluminescent materials and devices
US10862054B2 (en) 2016-06-20 2020-12-08 Universal Display Corporation Organic electroluminescent materials and devices
US11482683B2 (en) 2016-06-20 2022-10-25 Universal Display Corporation Organic electroluminescent materials and devices
US10672997B2 (en) 2016-06-20 2020-06-02 Universal Display Corporation Organic electroluminescent materials and devices
CN106243014A (en) * 2016-07-12 2016-12-21 长春海谱润斯科技有限公司 A kind of benzopyrene derivant and its preparation method and application
CN106336408A (en) * 2016-08-24 2017-01-18 长春海谱润斯科技有限公司 Naphthothioxanthene derivative and preparation method and application thereof
US10608186B2 (en) 2016-09-14 2020-03-31 Universal Display Corporation Organic electroluminescent materials and devices
US10680187B2 (en) 2016-09-23 2020-06-09 Universal Display Corporation Organic electroluminescent materials and devices
US11196010B2 (en) 2016-10-03 2021-12-07 Universal Display Corporation Organic electroluminescent materials and devices
US11011709B2 (en) 2016-10-07 2021-05-18 Universal Display Corporation Organic electroluminescent materials and devices
US20180130956A1 (en) 2016-11-09 2018-05-10 Universal Display Corporation Organic electroluminescent materials and devices
US10680188B2 (en) 2016-11-11 2020-06-09 Universal Display Corporation Organic electroluminescent materials and devices
US11780865B2 (en) 2017-01-09 2023-10-10 Universal Display Corporation Organic electroluminescent materials and devices
US10844085B2 (en) 2017-03-29 2020-11-24 Universal Display Corporation Organic electroluminescent materials and devices
US10944060B2 (en) 2017-05-11 2021-03-09 Universal Display Corporation Organic electroluminescent materials and devices
US12098157B2 (en) 2017-06-23 2024-09-24 Universal Display Corporation Organic electroluminescent materials and devices
US11228010B2 (en) 2017-07-26 2022-01-18 Universal Display Corporation Organic electroluminescent materials and devices
US11744142B2 (en) 2017-08-10 2023-08-29 Universal Display Corporation Organic electroluminescent materials and devices
US20190161504A1 (en) 2017-11-28 2019-05-30 University Of Southern California Carbene compounds and organic electroluminescent devices
EP3492480B1 (en) 2017-11-29 2021-10-20 Universal Display Corporation Organic electroluminescent materials and devices
US11937503B2 (en) 2017-11-30 2024-03-19 Universal Display Corporation Organic electroluminescent materials and devices
CN111344289A (en) * 2017-12-27 2020-06-26 广州华睿光电材料有限公司 Nitrogen-containing heterocyclic compound, high polymer, mixture, composition and application thereof
US11542289B2 (en) 2018-01-26 2023-01-03 Universal Display Corporation Organic electroluminescent materials and devices
US20200075870A1 (en) 2018-08-22 2020-03-05 Universal Display Corporation Organic electroluminescent materials and devices
CN109293490B (en) * 2018-09-19 2021-07-09 信阳师范学院 Benzoyl spiro arene steric hindrance type luminescent material and preparation method thereof
US11737349B2 (en) 2018-12-12 2023-08-22 Universal Display Corporation Organic electroluminescent materials and devices
US11780829B2 (en) 2019-01-30 2023-10-10 The University Of Southern California Organic electroluminescent materials and devices
US20200251664A1 (en) 2019-02-01 2020-08-06 Universal Display Corporation Organic electroluminescent materials and devices
JP2020158491A (en) 2019-03-26 2020-10-01 ユニバーサル ディスプレイ コーポレイション Organic electroluminescent materials and devices
US20210032278A1 (en) 2019-07-30 2021-02-04 Universal Display Corporation Organic electroluminescent materials and devices
US20210047354A1 (en) 2019-08-16 2021-02-18 Universal Display Corporation Organic electroluminescent materials and devices
CN110526938B (en) * 2019-08-26 2022-09-09 武汉华星光电半导体显示技术有限公司 Deep blue photo-thermal activation delayed fluorescence material, preparation method thereof and electroluminescent device
US20210135130A1 (en) 2019-11-04 2021-05-06 Universal Display Corporation Organic electroluminescent materials and devices
CN112812023B (en) * 2019-11-15 2023-10-03 石家庄诚志永华显示材料有限公司 Organic compound, material for organic electroluminescent device, and organic electroluminescent device
US20210217969A1 (en) 2020-01-06 2021-07-15 Universal Display Corporation Organic electroluminescent materials and devices
US20220336759A1 (en) 2020-01-28 2022-10-20 Universal Display Corporation Organic electroluminescent materials and devices
EP3937268A1 (en) 2020-07-10 2022-01-12 Universal Display Corporation Plasmonic oleds and vertical dipole emitters
US20220158096A1 (en) 2020-11-16 2022-05-19 Universal Display Corporation Organic electroluminescent materials and devices
US20220165967A1 (en) 2020-11-24 2022-05-26 Universal Display Corporation Organic electroluminescent materials and devices
US20220162243A1 (en) 2020-11-24 2022-05-26 Universal Display Corporation Organic electroluminescent materials and devices
US20220271241A1 (en) 2021-02-03 2022-08-25 Universal Display Corporation Organic electroluminescent materials and devices
EP4059915A3 (en) 2021-02-26 2022-12-28 Universal Display Corporation Organic electroluminescent materials and devices
EP4060758A3 (en) 2021-02-26 2023-03-29 Universal Display Corporation Organic electroluminescent materials and devices
US20220298192A1 (en) 2021-03-05 2022-09-22 Universal Display Corporation Organic electroluminescent materials and devices
US20220298190A1 (en) 2021-03-12 2022-09-22 Universal Display Corporation Organic electroluminescent materials and devices
US20220298193A1 (en) 2021-03-15 2022-09-22 Universal Display Corporation Organic electroluminescent materials and devices
US20220340607A1 (en) 2021-04-05 2022-10-27 Universal Display Corporation Organic electroluminescent materials and devices
EP4075531A1 (en) 2021-04-13 2022-10-19 Universal Display Corporation Plasmonic oleds and vertical dipole emitters
US20220352478A1 (en) 2021-04-14 2022-11-03 Universal Display Corporation Organic eletroluminescent materials and devices
US20220407020A1 (en) 2021-04-23 2022-12-22 Universal Display Corporation Organic electroluminescent materials and devices
US20230006149A1 (en) 2021-04-23 2023-01-05 Universal Display Corporation Organic electroluminescent materials and devices
US20230133787A1 (en) 2021-06-08 2023-05-04 University Of Southern California Molecular Alignment of Homoleptic Iridium Phosphors
EP4151699A1 (en) 2021-09-17 2023-03-22 Universal Display Corporation Organic electroluminescent materials and devices
US20240343970A1 (en) 2021-12-16 2024-10-17 Universal Display Corporation Organic electroluminescent materials and devices
EP4231804A3 (en) 2022-02-16 2023-09-20 Universal Display Corporation Organic electroluminescent materials and devices
US20230337516A1 (en) 2022-04-18 2023-10-19 Universal Display Corporation Organic electroluminescent materials and devices
US20230389421A1 (en) 2022-05-24 2023-11-30 Universal Display Corporation Organic electroluminescent materials and devices
EP4293001A1 (en) 2022-06-08 2023-12-20 Universal Display Corporation Organic electroluminescent materials and devices
US20240016051A1 (en) 2022-06-28 2024-01-11 Universal Display Corporation Organic electroluminescent materials and devices
US20240107880A1 (en) 2022-08-17 2024-03-28 Universal Display Corporation Organic electroluminescent materials and devices
US20240188316A1 (en) 2022-10-27 2024-06-06 Universal Display Corporation Organic electroluminescent materials and devices
US20240196730A1 (en) 2022-10-27 2024-06-13 Universal Display Corporation Organic electroluminescent materials and devices
US20240188419A1 (en) 2022-10-27 2024-06-06 Universal Display Corporation Organic electroluminescent materials and devices
US20240188319A1 (en) 2022-10-27 2024-06-06 Universal Display Corporation Organic electroluminescent materials and devices
US20240180025A1 (en) 2022-10-27 2024-05-30 Universal Display Corporation Organic electroluminescent materials and devices
US20240247017A1 (en) 2022-12-14 2024-07-25 Universal Display Corporation Organic electroluminescent materials and devices

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110198577A1 (en) * 2008-10-06 2011-08-18 Sony Corporation Organic electroluminescent element and display device
CN102372670A (en) * 2010-08-20 2012-03-14 清华大学 Arylamine compounds containing arylpyridine groups and application of arylamine compounds containing arylpyridine group
CN103172554A (en) * 2011-12-26 2013-06-26 昆山维信诺显示技术有限公司 Organic compound and application thereof
CN103664906A (en) * 2012-09-26 2014-03-26 昆山维信诺显示技术有限公司 6, 6-dimethyl-6H- benzo [cd] pyrene derivative and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110198577A1 (en) * 2008-10-06 2011-08-18 Sony Corporation Organic electroluminescent element and display device
CN102372670A (en) * 2010-08-20 2012-03-14 清华大学 Arylamine compounds containing arylpyridine groups and application of arylamine compounds containing arylpyridine group
CN103172554A (en) * 2011-12-26 2013-06-26 昆山维信诺显示技术有限公司 Organic compound and application thereof
CN103664906A (en) * 2012-09-26 2014-03-26 昆山维信诺显示技术有限公司 6, 6-dimethyl-6H- benzo [cd] pyrene derivative and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3533788A1 (en) * 2018-02-28 2019-09-04 Novaled GmbH Organic material for an electronic optoelectronic device and electronic device comprising the organic material
WO2019166206A1 (en) * 2018-02-28 2019-09-06 Novaled Gmbh Organic material for an electronic optoelectronic device and electronic device comprising the organic material

Also Published As

Publication number Publication date
CN103508940A (en) 2014-01-15

Similar Documents

Publication Publication Date Title
CN103508940B (en) 6, 6-disubstituted-6-H-benzo[cd]pyrene derivatives and intermediates, and preparation methods and applications of derivatives and intermediates
CN108290865B (en) Heterocyclic compound and organic light-emitting device using the same
CN100425599C (en) Organic electroluminescent material and its application
CN110903311B (en) Polycyclic organoboron derivatives and electronic devices
CN110981899B (en) Polycyclic organoboron derivatives and electronic devices
WO2007069847A1 (en) Novel imidazoquinazoline derivative, process for preparing the same, and organic electronic device using the same
WO2008069586A1 (en) New fluorene derivatives and organic electronic device using the same
CN113150002B (en) Organic compound and organic electroluminescent device
KR102068859B1 (en) Hetero-cyclic compound and organic light emitting device comprising the same
CN111662309B (en) Compound with multi-heterocyclic structure and application thereof
CN103508836A (en) 6, 6-disubstituted-6-H-benzo[cd]pyrene derivative, and preparation method and applications thereof
CN110776496A (en) 3, 4-diazaspiro fluorene derivative and synthesis method thereof, and electronic device containing 3, 4-diazaspiro fluorene derivative
CN111635391A (en) Fluorene compound and electronic device
CN111620853A (en) Organic electroluminescent material and device thereof
CN114249738A (en) Electroluminescent material and device
US10476006B2 (en) Compound and organic electronic device using the same
CN111116561B (en) Compound containing condensed ring structure, application thereof and organic electroluminescent device
CN103172554B (en) One class organic compound and application thereof
CN103172524B (en) One class organic compound and application thereof
CN108349987A (en) Benzimidazole fused heteroaromatics
CN113372289A (en) Organic electronic material containing phenanthrene azole compound and preparation method and application thereof
CN102532002A (en) Tetrahydroanthracene compound containing terpyridyl group and application thereof
CN113149964A (en) Compound containing conjugated condensed ring aromatic structure, application thereof and organic electroluminescent device
EP4265619A1 (en) Heterocyclic compound and organic light-emitting device comprising same
CN115368392A (en) Polycyclic aromatic compound, reactive compound, material for organic device, ink composition, and organic electroluminescent element

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant