CN114621269B - Condensed ring aromatic compound and application thereof in electroluminescent device - Google Patents

Condensed ring aromatic compound and application thereof in electroluminescent device Download PDF

Info

Publication number
CN114621269B
CN114621269B CN202011447096.8A CN202011447096A CN114621269B CN 114621269 B CN114621269 B CN 114621269B CN 202011447096 A CN202011447096 A CN 202011447096A CN 114621269 B CN114621269 B CN 114621269B
Authority
CN
China
Prior art keywords
ring
single bond
formula
synthesis
compound
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
CN202011447096.8A
Other languages
Chinese (zh)
Other versions
CN114621269A (en
Inventor
乔娟
薛杰
徐靖一
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
Original Assignee
Tsinghua University
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 filed Critical Tsinghua University
Priority to CN202011447096.8A priority Critical patent/CN114621269B/en
Publication of CN114621269A publication Critical patent/CN114621269A/en
Application granted granted Critical
Publication of CN114621269B publication Critical patent/CN114621269B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/027—Organoboranes and organoborohydrides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
    • C09K2211/1085—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with other heteroatoms

Landscapes

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

Abstract

The invention relates to a condensed ring aromatic compound and application thereof. The compound has a structure shown in the following formula I or formula II. When the compound is used as a luminescent layer material in an organic electroluminescent device, deep red/near infrared luminescence can be realized, high-efficiency electroluminescence and high spectral color purity are shown, and the best technical effect of narrow luminescent half-peak width of the device is obtained.

Description

Condensed ring aromatic compound and application thereof in electroluminescent device
Technical Field
The invention relates to a novel organic compound, in particular to a condensed ring structure molecule with a plurality of electron donating and electron withdrawing groups, and also relates to application of the compound in electroluminescent devices.
Background
Near infrared luminescent materials have been widely used in the fields of biological imaging, sensors, electronic communication, night vision, etc., and have been widely paid attention to by researchers. Taking biological imaging as an example, compared with the traditional techniques such as nuclear magnetic resonance imaging, CT imaging and the like, the fluorescent imaging technology using the near infrared material has the advantages of high sensitivity, high feedback speed, no harm to radiation, low price and the like, so the technology is rapidly developed. For fluorescence imaging, with the increase of the wavelength of luminescent molecules, photon scattering and autofluorescence phenomena caused by biological tissues can be obviously reduced, so that the signal-to-noise ratio and the penetration depth in the biological tissues are greatly improved.
The material capable of realizing near infrared luminescence mainly comprises single-wall carbon nanotubes, organic micromolecular dyes, quantum dot materials, conjugated polymers and rare earth doped nano particles. Compared with other types of materials, the organic micromolecular material has the advantages of high discharge speed and low toxicity. Meanwhile, for decades, organic Light-Emitting Diodes (OLEDs) based on Organic materials have been rapidly advanced. Compared with the traditional inorganic luminescent material, the organic luminescent material is more flexible in molecular design, can regulate and control various performance indexes such as thermal stability, luminescent property, conductivity property and the like of molecules through modification and reconstruction of molecular structures, and meanwhile, many organic materials also have high luminescent quantum efficiency.
Unlike photoexcitation, only 25% of total excitons generated by electrons and holes injected from the cathode and anode under photoexcitation are singlet excitons, and the remaining 75% are triplet excitons. The most primitive OLED uses traditional fluorescent materials, and cannot utilize triplet excitons accounting for 75% of the total exciton number, so its external quantum efficiency (External Quamtum Efficiency, EQE) is often difficult to break through by 5%. In order to solve the triplet exciton utilization problem, a second generation OLED material was developed since 1998, which is structurally characterized by a transition metal complex based on noble metals (such as iridium, platinum, osmium, etc.). Due to the heavy atom effect of the central noble metal, the material can effectively utilize triplet excitons to emit phosphorescence, so that the utilization rate of the excitons is 100%. However, the high-efficiency phosphorescent material has high cost of noble metal and small resource quantity, and must be limited in long-term application. Since 2011, the Adachi teaching at university of ninety japan reported OLEDs based on purely organic thermally activated delayed fluorescence (Thermally Activated Delayed Fluorescence, TADF) materials. The TADF material can convert triplet excitons into singlet excitons by means of room temperature, thereby emitting delayed fluorescence, and further realizing 100% exciton utilization rate. Therefore, the TADF material has a series of advantages of low cost, rich sources and the like, and becomes a third-generation OLED material.
With rapid development in recent years, the external quantum efficiency of both blue and green TADF materials has broken through 30%, while the efficiency of deep red/near infrared TADF materials has a great gap in comparison, which is mainly caused by two reasons: one is that according to the energy gap rule, as the red shift of the luminescence wavelength, i.e. the energy gap between the first excited singlet state and the ground state decreases, the non-radiative transition rate increases rapidly in an exponential form; on the other hand, the strong donor-acceptor structure introduced for realizing luminescence red shift can lead to low radiation transition rate, which is unfavorable for efficient luminescence, and meanwhile, the intrinsic strong charge transfer excited state property can lead the half-peak width of the luminescence spectrum to reach more than 80nm, thereby seriously reducing the color purity. Therefore, there is an urgent need to design a deep red/near infrared organic electroluminescent material with high color purity and high efficiency.
Disclosure of Invention
The invention aims to solve the problems of low quantity of deep red/near infrared organic luminescent materials and devices with high color purity and high efficiency in the prior art, and provides a condensed ring structure molecule with a plurality of electron donating and electron withdrawing groups at the same time. Meanwhile, the fused ring structure molecule provided by the invention has a rigid parallel ring structure, and is favorable for realizing high stability and long service life.
Specifically, the invention provides a condensed ring aromatic compound, which has a structure shown in the following formula I or formula II:
in the formula I, ar1 ring, ar2 ring, ar3 ring, ar4 ring, ar5 ring and Ar6 ring each independently represent one of a substituted or unsubstituted C6-C60 aromatic ring and a substituted or unsubstituted C4-C60 heteroaromatic ring;
X 1 、X 2 、X 3 、X 4 each independently selected from a single bond or any of the structures shown below, "×" represents the access bond position of a group:
n1, n2, n3, n4 are each independently 1 or 0;
in the formula II, ar7 ring, ar8 ring, ar9 ring, ar10 ring, ar11 ring, ar12 ring, ar13 ring and Ar14 ring each independently represents one of a substituted or unsubstituted C6-C60 aromatic ring and a substituted or unsubstituted C4-C60 heteroaromatic ring;
X 5 、X 6 、X 7 、X 8 each independently selected from a single bond or any of the structures shown below, "×" represents the access bond position of a group:
n5, n6, n7, n8 are each independently 1 or 0;
when a substituent pattern is present on Ar1 ring, ar2 ring, ar3 ring, ar4 ring, ar5 ring, ar6 ring, ar7 ring, ar8 ring, ar9 ring, ar10 ring, ar11 ring, ar12 ring, ar13 ring, ar14 ring, each independently represents a mono-substituted to maximum permissible substituent group, and adjacent two substituent groups may be linked by a single bond to form a ring, each independently selected from deuterium, halogen, cyano, C1-C36 chain alkyl, C1-C36 alkenyl, C1-C36 chain alkynyl, C3-C36 cycloalkyl, C4-C36 cycloalkenyl, C4-C36 cycloalkynyl, C1-C30 alkoxy, C1-C30 thioalkoxy, carbonyl, carboxyl, nitro, silicon-based, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C8-C60 aryl, C6-C60 aryloxy, C2-C60 monocyclic heteroaryl, or a combination of two fused rings.
Further, in the formula I and the formula II of the invention, each of the Ar1 ring, the Ar2 ring, the Ar3 ring, the Ar4 ring, the Ar5 ring, the Ar6 ring, the Ar7 ring, the Ar8 ring, the Ar9 ring, the Ar10 ring, the Ar11 ring, the Ar12 ring, the Ar13 ring and the Ar14 ring is independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidinyl and substituted or unsubstituted pyrazinyl;
preferably, the Ar1 ring, ar2 ring, ar3 ring, ar4 ring, ar5 ring, ar6 ring, ar7 ring, ar8 ring, ar9 ring, ar10 ring, ar11 ring, ar12 ring, ar13 ring, ar14 ring are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrazinyl;
when substituents are present on the above groups, the substituents are each independently selected from one of deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 halogenated aryl, C8-C60 fused ring aryl, C6-C60 aryloxy, C2-C60 monocyclic heteroaryl, C4-C60 fused ring heteroaryl.
Still further, when substituents are present on the Ar1 ring, ar2 ring, ar3 ring, ar4 ring, ar5 ring, ar6 ring, ar7 ring, ar8 ring, ar9 ring, ar10 ring, ar11 ring, ar12 ring, ar13 ring, ar14 ring in formulas I and II, the substituents are each independently selected from deuterium or from a combination of one or both of the following groups:
methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2-trifluoroethyl, 2-dicyanovinyl, phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, benzophenanthryl, pyrenyl,a group, perylene group, fluoranthenyl group, naphthacene group, pentacene group, benzopyrene group, biphenyl group, terphenyl group, tetrabiphenyl group, fluorenyl group, spirobifluorenyl group, dihydrophenanthrenyl group, dihydropyrenyl group, tetrahydropyrenyl group, cis-or trans-indenofluorenyl group, trimeric indenyl group, spirotrimeric indenyl group, spiroheterotrimeric indenyl group, furyl group, benzofuryl group, isobenzofuryl group, dibenzofuryl group, thienyl group, benzothienyl group, isobenzothienyl group, dibenzothienyl group, pyrrolyl group, isoindolyl group, carbazolyl group, indenocarzolyl group, pyridyl group, quinolyl group, isoquinolyl group, acridinyl group, phenanthridinyl group, and the like benzo-5, 6-quinolinyl, benzo-6, 7-quinolinyl, benzo-7, 8-quinolinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, napthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, thienyl, benzoxazolyl, naphthyrideazolyl, anthracenozolyl, phenanthroazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazaanthracenyl, 2, 7-diazapyrenyl, 2, 3-diazapyrenyl, 1, 6-diazapyrenyl, 1, 8-diazapyrenyl, 4,5,9, 10-tetraazaperylene, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarboline, phenanthroline, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazole, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylacridyl, diarylamino, adamantyl, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidine, methoxy, silicon, cyano, fluorine, chlorine.
Preferably, the condensed ring aromatic compound of the present invention has a structure represented by the following formula I-1 or formula II-1:
in the formula I-1, Z 1 -Z 16 Each independently selected from N or CR 1 ，R 1 One selected from hydrogen, deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 halogenated aryl, C8-C60 condensed ring aryl, C6-C60 aryloxy, C2-C60 monocyclic heteroaryl, C4-C60 condensed ring heteroaryl, when Z 1 -Z 16 Wherein two adjacent rings are present and are located on the same ring are each selected from CR 1 When the two R's are 1 The two can be connected into a ring through a single bond; the X is 1 、X 2 、X 3 、X 4 The definitions of n1, n2, n3, n4 are the same as in formula I;
in the formula I-1, Y 1 -Y 8 Each independently selected from C, CR 2 Or N, and Y when N1 is 1 1 And Y 2 All are C, when n2 isY at 1 3 And Y 4 All are C, Y when n3 is 1 5 And Y 6 All are C, Y when n4 is 1 7 And Y 8 All are C, R 2 One selected from deuterium, halogen, cyano, C1-C4 chain alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;
in formula II-1, Z 21 -Z 42 Each independently selected from N or CR 3 ，R 3 One selected from hydrogen, deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 halogenated aryl, C8-C60 condensed ring aryl, C6-C60 aryloxy, C2-C60 monocyclic heteroaryl, C4-C60 condensed ring heteroaryl, when Z 21 -Z 42 Wherein two adjacent rings are present and are located on the same ring are each selected from CR 2 When the two R's are 2 The two can be connected into a ring through a single bond; the X is 5 、X 6 、X 7 、X 8 N5, n6, n7, n8 are as defined in formula II;
in formula II-1, Y 21 -Y 28 Each independently selected from C, CR 4 Or N, and Y when N5 is 1 21 And Y 22 All are C, Y when n6 is 1 23 And Y 24 All are C, Y when n7 is 1 25 And Y 26 All are C, Y when n8 is 1 27 And Y 28 All are C, R 4 One selected from deuterium, halogen, cyano, C1-C4 chain alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;
preferably, said R 1 And R is 3 Each independently selected from one of hydrogen, deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tert-butyl, trifluoromethyl, pentafluoroethyl, phenyl, methyl-substituted phenyl, trifluoromethyl-substituted phenyl, carbazolyl, N-diphenylamino, p-N, N-diphenylaminophenyl; the R is 2 And R is 4 Each independently selected from hydrogen, deuterium, cyano, methyl, ethyl, methoxy, isoPropyl, tert-butyl, trifluoromethyl, pentafluoroethyl.
More preferably, the condensed ring aromatic compound of the present invention has a structure represented by the following formula I-2 or formula II-2:
in formula I-2, R1-R16 are each independently selected from one of hydrogen, deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 haloaryl, C8-C60 fused ring aryl, C6-C60 aryloxy, C2-C60 monocyclic heteroaryl, C4-C60 fused ring heteroaryl, and adjacent two of R1-R16 groups attached to the same benzene ring may be linked by a single bond; the X is 1 、X 2 、X 3 、X 4 N1, n2, n3, n4 are as defined in formula I, Y 1 -Y 8 Is as defined in formula I-1;
in the formula I-2, preferably, R1, R8, R9 and R16 are hydrogen or deuterium, and R2-R7 and R10-R15 are each independently selected from one of deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 halogenated aryl, C8-C60 fused ring aryl, C6-C60 aryloxy, C2-C60 monocyclic heteroaryl and C4-C60 fused ring heteroaryl;
in the formula I-2, more preferably, each R1-R16 is independently selected from one of hydrogen, deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tert-butyl, trifluoromethyl, pentafluoroethyl, phenyl, methyl-substituted phenyl, trifluoromethyl-substituted phenyl, carbazolyl, N-diphenylamino, p-N, N-diphenylaminophenyl;
in the formula I-2, more preferably, R1, R8, R9 and R16 are hydrogen or deuterium, and R2-R7 and R10-R15 are each independently selected from one of deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tertiary butyl, trifluoromethyl, pentafluoroethyl, phenyl, methyl-substituted phenyl, trifluoromethyl-substituted phenyl, carbazolyl, N-diphenylamino and p-N, N-diphenylaminophenyl;
In formula II-2, R21-R42 are each independently selected from one of hydrogen, deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 haloaryl, C8-C60 fused ring aryl, C6-C60 aryloxy, C2-C60 monocyclic heteroaryl, C4-C60 fused ring heteroaryl, and adjacent two of R21-R42 groups attached to the same benzene ring may be linked by a single bond; the X is 5 、X 6 、X 7 、X 8 N5, n6, n7, n8 are as defined in formula II, Y 21 -Y 28 Is as defined in formula II-1;
in formula II-2, preferably, R21, R28, R29, R31, R32, R39, R40, R42 are hydrogen or deuterium, and R22-R27, R30, R33-R38, R41 are each independently selected from one of deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 halogenated aryl, C8-C60 fused ring aryl, C6-C60 aryloxy, C2-C60 monocyclic heteroaryl, C4-C60 fused ring heteroaryl;
Still more preferably, in formula II-2, each R21-R42 is independently selected from one of hydrogen, deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tert-butyl, trifluoromethyl, pentafluoroethyl, phenyl, methyl-substituted phenyl, trifluoromethyl-substituted phenyl, carbazolyl, N-diphenylamino, p-N, N-diphenylaminophenyl;
more preferably, in formula II-2, R21, R28, R29, R31, R32, R39, R40, R42 are hydrogen or deuterium, and R22-R27, R30, R33-R38, R41 are each independently selected from one of deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tert-butyl, trifluoromethyl, pentafluoroethyl, phenyl, methyl-substituted phenyl, trifluoromethyl-substituted phenyl, carbazolyl, N-diphenylamino, p-N, N-diphenylaminophenyl.
Still further, in formulas I, I-1 and I-2, the n1, n2, n3, n4 are all 1, and X 1 、X 2 、X 3 、X 4 Are all single bond structures;
alternatively, n1, n2, n3, n4 are all 1, X 1 、X 2 、X 3 、X 4 All have the structure shown in A1;
alternatively, n1, n2, n3, n4 are all 1, X 1 、X 2 、X 3 、X 4 All have the structure shown as A2;
alternatively, n1, n2, n3, n4 are all 1, X 1 、X 2 、X 3 、X 4 All have the structure shown in A3;
or, the structures of n1, n2, n3 and n4 are all 0;
Alternatively, n1, n2, n3, n4 are all 1, X 1 And X is 3 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n2, n3, n4 are all 1, X 1 And X is 4 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n2, n3, n4 are all 1, X 1 And X is 3 Is the same and is selected from one of single bond, A1, A2 or A3, and X 2 And X is 4 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n2, n3, n4 are all 1, X 1 And X is 4 Is the same and is selected from one of single bond, A1, A2 or A3, and X 2 And X is 3 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n3 are 1, n2, n4 are 0, and X is 1 And X is 3 Identical, simultaneously selected from single bondsOne of the formulae A1, A2 or A3;
alternatively, n1, n4 are 1, n2, n3 are 0, and X is 1 And X is 4 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
in the formula II, the formula II-1 and the formula II-2, n5, n6, n7 and n8 are all 1, and X 5 、X 6 、X 7 、X 8 Are all single bond structures;
alternatively, the n5, n6, n7, n8 are all 1, X 5 、X 6 、X 7 、X 8 All have the structure shown in A1;
alternatively, the n5, n6, n7, n8 are all 1, X 5 、X 6 、X 7 、X 8 All have the structure shown as A2;
alternatively, the n5, n6, n7, n8 are all 1, X 5 、X 6 、X 7 、X 8 All have the structure shown in A3;
or, the structures of n5, n6, n7 and n8 are all 0;
alternatively, n5, n6, n7, n8 are all 1, X 5 And X is 7 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n5, n6, n7, n8 are all 1, X 5 And X is 8 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n5, n6, n7, n8 are all 1, X 5 And X is 7 Is the same and is selected from one of single bond, A1, A2 or A3, and X 6 And X is 8 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n5, n6, n7, n8 are all 1, X 5 And X is 8 Is the same and is selected from one of single bond, A1, A2 or A3, and X 6 And X is 7 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n5, n7 are 1, n6, n8 are 0, and X is 5 And X is 7 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, a subject is provided withN5 and n8 are 1, n6 and n7 are 0, and X is 5 And X is 8 And is the same as or simultaneously selected from one of single bond, formula A1, A2 or A3.
Further, the condensed ring aromatic compound of the present invention may preferably have a specific structure shown by the following C1 to C303, and these compounds are merely representative and do not limit the scope of the present invention.
/>
/>
/>
/>
/>
The application of the compound as a functional material in an organic electronic device comprises the following steps: organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, organic thin film solar cells, information labels, electronic artificial skin sheets, sheet scanners or electronic papers, preferably organic electroluminescent devices.
The invention also provides an organic electroluminescent device, which comprises a substrate, and comprises a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layers comprise compounds shown in any one of the formula I, the formula II, the formula I-1, the formula II-1, the formula I-2 and the formula II-2, and more preferably, the organic layers comprise specific compounds shown in any one of the C1-C303.
Specifically, an embodiment of the present invention provides an organic electroluminescent device including a substrate, and an anode layer, a plurality of light emitting functional layers, and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transmission layer, a light-emitting layer and an electron transmission layer, wherein the hole injection layer is formed on the anode layer, the hole transmission layer is formed on the hole injection layer, the cathode layer is formed on the electron transmission layer, and the light-emitting layer is arranged between the hole transmission layer and the electron transmission layer; preferably, the light-emitting layer contains the compound of the general formula shown in any one of the above formula I, formula II, formula I-1, formula II-1, formula I-2 and formula II-2. Further preferably, the light-emitting layer contains a specific compound represented by any one of the above-mentioned C1 to C303.
The specific reasons why the compounds of the structures of the formulae I, II, I-1, II-1, I-2 and II-2 of the present invention can further achieve excellent technical effects are not clear, the specific reasons for the excellent properties of the materials used as light emitting layers in organic electroluminescent devices are not clear, and the following is the inventors' conjecture, but these conjectures do not limit the scope of the present invention.
The rigid condensed ring structural molecule designed by the invention has a plurality of electron-withdrawing units and a plurality of electron-donating units, so that the charge transfer between a donor unit and an acceptor unit in the molecule can be effectively promoted, and the excited state energy can be effectively stabilized; on the other hand, the molecules have relatively planar condensed ring large pi conjugated structures, which can realize effective conjugated delocalization of pi electrons on aromatic rings, so that the luminescence of the molecules can effectively realize deep red/near infrared luminescence. Because the central skeleton structure of the molecule designed by the invention has a structure adjacent to electron-withdrawing boron atoms and electron-donating nitrogen atoms, the molecular orbit still has the characteristic of multiple resonances, which is favorable for realizing small recombination energy and non-radiative transition rate, and realizing high luminous efficiency and narrow half-peak width. More importantly, the molecules designed by the invention have a rigid structure, on one hand, the vibration and rotation of the molecules can be effectively inhibited, and the recombination energy is reduced, so that the molecules have narrower half-peak width and lower non-radiative transition rate; on the other hand, the front-line orbitals of the rigid condensed ring molecules are distributed on the whole condensed ring structure, so that the excited state of the rigid condensed ring molecules has high transition dipole and high radiation transition rate, and the high-efficiency luminescence is realized. At the same time, the rigid structure endows the molecules with high stability, so that the material has long service life when in use, and the corresponding device also has long service life. Further, by adopting single bonds or weak electron donating A1, A2 or A3 bridging groups in four X groups on two sides of the molecule, a rigid closed-loop structure can be formed, so that the problem of structural relaxation caused by electron transition is further suppressed, high-efficiency luminescence is facilitated, and meanwhile, the bond energy of the molecule can be further improved by the formation of the closed-loop structure, so that the stability of the molecule is improved. In terms of electronic structure, the adoption of a single bond or a weak electron-donating A1, A2 or A3 bridging group has less influence on the electronic structure of the central framework, so that the excellent luminescent property of the central framework is maintained; on the other hand, the introduction of the single bond and the A1, A2 or A3 bridging group with weak electron supply can effectively increase the delocalization degree and the conjugation degree of electrons on the parent nucleus, thereby being beneficial to realizing the further red shift of the luminescence of the material and promoting the radiation transition to realize the high-efficiency luminescence. Furthermore, the four bridging positions on two sides of the molecule can be X groups or X-free groups with different structure types, and the electronic structure in the molecule can be regulated and controlled by the combined optimization design of single bond, A1, A2, A3 or X-free groups on the four bridging positions on two sides of the molecule, so that the effective regulation and control on the photophysical property of the molecule can be realized. It is worth mentioning that such rigid condensed ring structure molecules possess excellent bipolar transport properties due to the simultaneous electron donating nitrogen atoms and electron withdrawing boron atoms. Meanwhile, the HOMO and LUMO energy levels of the molecules can be regulated and controlled through the combination and optimization of the groups at the bridging positions, so that the energy levels of the molecules are more matched with the energy levels of the transmission layer materials in the device, and the higher efficiency of the device is realized. In addition, the rigid condensed ring structure derivative can further regulate the physical and chemical properties of the molecule through substituent groups on each Ar ring in the mother nucleus.
The organic electroluminescent device adopting the aromatic compound with the rigid condensed ring structure as the luminescent layer material has the excellent technical effects of high luminous efficiency, high spectral color purity, narrow half-peak width, long service life of the device and the like.
Drawings
FIG. 1 is a graph showing the ultraviolet-visible absorption spectrum and fluorescence spectrum of the compound C1 prepared in synthetic example 1 of the present invention;
FIG. 2 is an electroluminescence spectrum of an OLED1 of the organic electroluminescent device prepared in example 1 of the device of the present invention;
fig. 3 is an external quantum efficiency-current density curve of the organic electroluminescent device OLED1 device prepared in device example 1 according to the present invention.
Detailed Description
The present invention will be described in further detail below with reference to the drawings and detailed description for the purpose of enabling those skilled in the art to understand the invention better.
Compound synthesis embodiment:
specific methods for preparing the above novel compounds of the present invention will be described below by way of example with reference to a plurality of synthesis examples, but the preparation method of the present invention is not limited to these synthesis examples.
All compounds of the synthesis methods not mentioned in the examples of the present invention are commercially available starting products. The solvents and reagents used in the present invention, such as ethyl acetate, toluene, sodium carbonate, etc., may be purchased from domestic chemical product markets, such as from the national pharmaceutical group reagent company, TCI company, shanghai pi-get pharmaceutical company, carboline reagent company, etc. In addition, the person skilled in the art can synthesize the compounds by known methods.
Compound synthesis examples
Synthesis example 1: synthesis of Compound C1
In this synthesis example, compound C1 was synthesized according to the following scheme.
1.70g (71 mmol) of sodium hydride and 60mL of dimethyl sulfoxide were charged into a 250mL three-necked flask. To this system was slowly added 7.27g (42 mmol) of o-bromophenol with stirring, followed by 4.72g (20 mmol) of 1, 4-dichloro-2, 3-dinitrobenzene in a three-necked flask. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 90℃for 2 hours under closed conditions. After the reaction is completed, after the reaction system is cooled to room temperature, pouring the reaction system into cold water, extracting and separating the reaction system by using ethyl acetate to obtain an organic layer, then continuously extracting and separating the water phase twice, merging the obtained organic phases, drying the organic phase by using anhydrous sodium sulfate, filtering to remove solid particles, and then performing rotary evaporation to remove an organic solvent. The crude product obtained was recrystallized from ethanol to give 8.21g of light brown solid with a yield of 80.5%.
36.33g (161.0 mmol) stannous chloride dihydrate and 200mL ethanol are added to a 250mL three-necked flask. To this system was slowly added 8.21g (16.1 mmol) of the intermediate obtained in the previous step with stirring. The gas in the three-necked flask was replaced with nitrogen, and then the reaction was stirred at 70℃for 2 hours under closed conditions. After the reaction was completed, when the reaction system was cooled to room temperature, it was poured into cold water, and an aqueous sodium hydroxide solution was added dropwise thereto to adjust the pH of the system to neutral. The organic layer was separated by extraction with diethyl ether, the aqueous phase was then extracted twice and separated, the organic phases obtained were combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and the organic solvent was removed by rotary evaporation. After rotary evaporation, a dark brown oily liquid was obtained 5.93g in 81.8% yield, which was not subjected to further purification because the product was unstable in air.
5.93g (13.17 mmol) of the intermediate obtained in the previous step, 3.46g of potassium carbonate (25 mmol) and 0.29g of copper powder (4.6 mmol) were charged into a 100mL round bottom flask, followed by 50mL of o-dichlorobenzene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 190℃for 24 hours under closed conditions. After the reaction is completed, when the reaction system is cooled to room temperature, insoluble solid particles in the system are filtered and removed, and the obtained solution is subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: ethyl acetate=1:1 (volume ratio). The white solid obtained by column chromatography was 2.76g and the yield was 72.6%.
2.76g (9.56 mmol) of the obtained intermediate, 2.13g (4.6 mmol) of 1, 4-dichloro-tetrabromobenzene, 0.14g (0.25 mmol) of bis-dibenzylideneacetone palladium, 0.15g (0.75 mmol) of tri-tert-butylphosphine, 4.89g (15 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=2:1 (volume ratio). The orange solid obtained by column chromatography was 2.67g and the yield was 72.2%.
2.67g (3.32 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 4.2mL (9.96 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5 hours at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2 hours. The temperature of the reaction system was lowered to-40℃and 0.95mL (9.96 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.72mL (15.94 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=5:1 (volume ratio). The dark purple solid obtained by column chromatography was 1.04g with a yield of 47.4%. MALDI-TOF-MS results: molecular ion peak: 662.14. elemental analysis results: theoretical value: c,76.18; h,2.44; b,3.26; n,8.46; o,9.66. Experimental values: c,76.19; h,2.43; b,3.25; n,8.45; o,9.68.
Synthesis example 2: synthesis of Compound C4
This example is substantially identical to synthetic example 1, except that: in this case, the o-bromophenol is replaced by an equivalent amount of 5-trifluoromethyl-2-bromophenol. MALDI-TOF-MS results: molecular ion peak: 934.09. elemental analysis results: theoretical value: c,59.14; h,1.29; b,2.31; f,24.40; n,6.00; o,6.85. Experimental values: c,59.16; h,1.28; b,2.31; f,24.41; n,6.01; o,6.84.
Synthesis example 3: synthesis of Compound C9
This example is substantially identical to synthetic example 1, except that: in this case, the o-bromophenol is replaced by an equivalent amount of 5-isopropyl-2-bromophenol. MALDI-TOF-MS results: molecular ion peak: 830.32. elemental analysis results: theoretical value: c,78.09; h,4.85; b,2.60; n,6.75; o,7.71. Experimental values: c,78.07; h,4.84; b,2.61; n,6.76; o,7.72.
Synthesis example 4: synthesis of Compound C13
This example is substantially identical to synthetic example 1, except that: in this case, the o-bromophenol is replaced by an equivalent amount of 5-t-butyl-2-bromophenol. MALDI-TOF-MS results: molecular ion peak: 830.32. elemental analysis results: theoretical value: c,78.57; h,5.46; b,2.44; n,6.32; o,7.22. Experimental values: c,78.58; h,5.45; b,2.43; n,6.31; o,7.24.
Synthesis example 5: synthesis of Compound C16
This example is substantially identical to synthetic example 1, except that: in this case, the o-bromophenol is replaced by an equivalent amount of 5-methyl-2-bromophenol. MALDI-TOF-MS results: molecular ion peak: 718.20. elemental analysis results: theoretical value: c,76.91; h,3.37; b,3.01; n,7.80; o,8.91. Experimental values: c,76.91; h,3.36; b,3.00; n,7.81; o,8.92.
Synthesis example 6: synthesis of Compound C18
This example is substantially identical to synthetic example 1, except that: in this case, the o-bromophenol is replaced by an equivalent amount of 5-methoxy-2-bromophenol. MALDI-TOF-MS results: molecular ion peak: 782.18. elemental analysis results: theoretical value: c,70.62; h,3.09; b,2.76; n,7.16; o,16.36. Experimental values: c,70.61; h,3.09; b,2.75; n,7.17; o,16.37.
Synthesis example 7: synthesis of Compound C23
This example is substantially identical to synthetic example 1, except that: in this case, the o-bromophenol is replaced by an equivalent amount of 4-bromo-3-hydroxypyridine. MALDI-TOF-MS results: molecular ion peak: 666.12. elemental analysis results: theoretical value: c,68.51; h,1.82; b,3.25; n,16.82; o,9.61. Experimental values: c,68.50; h,1.82; b,3.24; n,16.83; o,9.62.
Synthesis example 8: synthesis of Compound C27
This example is substantially identical to synthetic example 1, except that: in this case, the o-bromophenol is replaced by an equivalent amount of 4-bromo-3 ',5' -bis (trifluoromethyl) - [1,1' -biphenyl ] -3-ol. MALDI-TOF-MS results: molecular ion peak: 1510.16. elemental analysis results: theoretical value: c,58.84; h,1.60; b,1.43; f,30.18; n,3.71; o,4.24. Experimental values: c,58.84; h,1.61; b,1.42; f,30.17; n,3.72; o,4.25.
Synthesis example 9: synthesis of Compound C32
Intermediate Z2 was first synthesized:
phenazine 4.0g (22.2 mmol) and 140mL of ethanol were added to a 500mL round bottom flask and the reaction system was heated to 85℃with stirring and nitrogen protection until the solution was clear. 46.6g (268 mmol) of sodium dithionite was dissolved in 200mL of deoxygenated deionized water, followed by addition to the reaction system and stirring under reflux for 2h. After the reaction is completed, the reaction system is cooled to room temperature, suction filtration is carried out, the filter cake is washed by deoxidized deionized water, and then the filter cake is placed into a vacuum oven. After drying, 3.72g of pale green solid was obtained in 92% yield.
3.72g (20.4 mmol) of the intermediate obtained in the previous step, 10.14g (44.88 mmol) of 2, 6-dichloro-1-bromobenzene, 0.23g (1.02 mmol) of palladium acetate, 1.30g (4.50 mmol) of tri-tert-butylphosphine tetrafluoroborate, 16.92g (122.4 mmol) of potassium carbonate and 50mL of toluene were charged into a 100mL three-necked flask. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed system of dichloromethane and water, and an organic phase is extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=1:4 (volume ratio). The yellow-brown solid obtained by column chromatography was 7.18g and the yield was 74.5%.
7.18g (15.2 mmol) of the intermediate obtained in the previous step, 15.5mL (30.4 mmol) of bromine and 350mL of toluene were charged into a 500mL round-bottomed flask, followed by stirring under reflux at 100℃under closed conditions for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature and suction filtration was performed, and the obtained solid was directly added to a 2000mL round bottom flask. To this flask was further added a magnet wrapped with about 50cm copper wire and 1.5L of methanol. The gas in the round bottom flask was replaced with nitrogen and then the reaction was stirred under reflux at 60 ℃ under closed conditions overnight. As the reaction proceeds, a yellow solid forms in solution. After the reaction is completed, the reaction system is cooled to room temperature, suction filtration is carried out, and 9.60g of solid is obtained after drying, and the yield is 80.2%.
2.94g (10.2 mmol) of the Z1 intermediate, 3.94g (5 mmol) of the Z2 intermediate, 0.14g (0.25 mmol) of bis-dibenzylideneacetone palladium, 0.15g (0.75 mmol) of tri-tert-butylphosphine, 4.89g (15 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=1:1 (volume ratio). The product was isolated by column chromatography to give 3.60g of a tan solid in 69.2% yield.
3.60g (3.46 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 4.3mL (10.38 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5h at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2h. The temperature of the reaction system was lowered to-40℃and 0.98mL (10.38 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.84mL (16.61 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=35:1 (volume ratio). The purple solid obtained by column chromatography was 1.24g, and the yield was 38.5%. MALDI-TOF-MS results: molecular ion peak: 934.21. elemental analysis results: theoretical value: c,77.15; h,2.37; b,4.63; n,9.00; o,6.85. Experimental values: c,77.14; h,2.36; b,4.63; n,9.01; o,6.86.
Synthesis example 10: synthesis of Compound C33
This example is substantially identical to synthetic example 9, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-methyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 962.24. elemental analysis results: theoretical value: c,77.40; h,2.72; b,4.49; n,8.73; o,6.65. Experimental values: c,77.40; h,2.71; b,4.48; n,8.74; o,6.66.
Synthesis example 11: synthesis of Compound C35
This example is substantially identical to synthetic example 9, except that: in this example, the raw material of o-bromophenol for synthesizing the Z1 intermediate and the raw material of 2, 6-dichloro-1-bromophenyl for synthesizing the Z2 intermediate were replaced with the same amounts of 5-methyl-2-bromophenol and 4-methyl-2, 6-dichloro-1-bromophenyl. MALDI-TOF-MS results: molecular ion peak: 1018.30. elemental analysis results: theoretical value: c,77.85; h,3.37; b,4.25; n,8.25; o,6.28. Experimental values: c,77.84; h,3.38; b,4.25; n,8.24; o,6.29.
Synthesis example 12: synthesis of Compound C38
This example is substantially identical to synthetic example 9, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was replaced with an equal amount of 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1070.18. elemental analysis results: theoretical value: c,69.59; h,1.88; b,4.04; f,10.65; n,7.85; o,5.98. Experimental values: c,69.58; h,1.87; b,4.04; f,10.66; n,7.84; o,5.99.
Synthesis example 13: synthesis of Compound C40
This example is substantially identical to synthetic example 9, except that: in this example, the raw material of o-bromophenol for synthesizing the Z1 intermediate and the raw material of 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate were replaced with the same amounts of 5-trifluoromethyl-2-bromophenol and 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1342.13. elemental analysis results: theoretical value: c,59.07; h,1.20; b,3.22; f,25.48; n,6.26; o,4.77. Experimental values: c,59.06; h,1.21; b,3.21; f,25.47; n,6.25; o,4.78.
Synthesis example 14: synthesis of Compound C43
This example is substantially identical to synthetic example 9, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was converted to an equivalent amount of 4-isopropyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1018.30. elemental analysis results: theoretical value: c,77.85; h,3.37; b,4.25; n,8.25; o,6.28. Experimental values: c,77.85; h,3.38; b,4.24; n,8.24; o,6.29.
Synthesis example 15: synthesis of Compound C45
This example is substantially identical to synthetic example 9, except that: in this example, the raw materials of o-bromophenol for synthesizing the Z1 intermediate and 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate were replaced with the same amounts of 5-isopropyl-2-bromophenol and 4-isopropyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1186.49. elemental analysis results: theoretical value: c,78.95; h,4.93; b,3.64; n,7.08; o,5.39. Experimental values: c,78.96; h,4.94; b,3.64; n,7.07; o,5.38.
Synthesis example 16: synthesis of Compound C48
This example is substantially identical to synthetic example 9, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-tert-butyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1046.33. elemental analysis results: theoretical value: c,78.06; h,3.66; b,4.13; n,8.03; o,6.12. Experimental values: c,78.05; h,3.66; b,4.12; n,8.04; o,6.13.
Synthesis example 17: synthesis of Compound C50
This example is substantially identical to synthetic example 9, except that: in this example, the raw materials of o-bromophenol for synthesizing the Z1 intermediate and 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate were replaced with the same amounts of 5-tert-butyl-2-bromophenol and 4-tert-butyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1270.58. elemental analysis results: theoretical value: c,79.40; h,5.55; b,3.40; n,6.61; o,5.04. Experimental values: c,79.38; h,5.54; b,3.40; n,6.62; o,5.05.
Synthesis example 18: synthesis of Compound C53
This example is substantially identical to synthetic example 9, except that: in this example, the raw material of o-bromophenol for synthesizing the Z1 intermediate and the raw material of 2, 6-dichloro-1-bromophenyl for synthesizing the Z2 intermediate were replaced with the same amounts of 5-methoxy-2-bromophenol and 4-methoxy-2, 6-dichloro-1-bromophenyl. MALDI-TOF-MS results: molecular ion peak: 1114.27. elemental analysis results: theoretical value: c,71.14; h,3.08; b,3.88; n,7.54; o,14.36. Experimental values: c,71.13; h,3.07; b,3.88; n,7.55; o,14.37.
Synthesis example 19: synthesis of Compound C61
This example is substantially identical to synthetic example 9, except that: in this example, the raw material o-bromophenol used for synthesizing the Z1 intermediate was replaced with an equivalent amount of 4-bromo-3 ',5' -bis (trifluoromethyl) - [1,1' -biphenyl ] -3-ol. MALDI-TOF-MS results: molecular ion peak: 1782.23. elemental analysis results: theoretical value: c,61.99; h,1.70; b,2.43; f,25.58; n,4.71; o,3.59. Experimental values: c,61.98; h,1.71; b,2.42; f,25.59; n,4.72; o,3.58.
Synthesis example 20: synthesis of Compound C65
In this synthesis example, compound C65 was synthesized according to the following scheme.
1.70g (71 mmol) of sodium hydride and 60mL of dimethyl sulfoxide were charged into a 250mL three-necked flask. To this system was slowly added 7.94g (42 mmol) of o-bromobenzenethiol with stirring, followed by 4.72g (20 mmol) of 1, 4-dichloro-2, 3-dinitrobenzene into a three-necked flask. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 90℃for 2 hours under closed conditions. After the reaction is completed, after the reaction system is cooled to room temperature, pouring the reaction system into cold water, extracting and separating the reaction system by using ethyl acetate to obtain an organic layer, then continuously extracting and separating the water phase twice, merging the obtained organic phases, drying the organic phase by using anhydrous sodium sulfate, filtering to remove solid particles, and then performing rotary evaporation to remove an organic solvent. The crude product obtained was recrystallized from ethanol to give 8.90g of light brown solid with a yield of 82.1%.
37.05g (164.2 mmol) of stannous chloride dihydrate and 200mL of ethanol were added to a 250mL three-necked flask. To this system was slowly added 8.90g (16.42 mmol) of the intermediate obtained in the previous step with stirring. The gas in the three-necked flask was replaced with nitrogen, and then the reaction was stirred at 70℃for 2 hours under closed conditions. After the reaction was completed, when the reaction system was cooled to room temperature, it was poured into cold water, and an aqueous sodium hydroxide solution was added dropwise thereto to adjust the pH of the system to neutral. The organic layer was separated by extraction with diethyl ether, the aqueous phase was then extracted twice and separated, the organic phases obtained were combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and the organic solvent was removed by rotary evaporation. After rotary evaporation, 6.37g of dark brown oily liquid are obtained in 80.5% yield, which is not further purified since the product is unstable in air.
6.37g (13.22 mmol) of the intermediate obtained in the previous step, 3.46g of potassium carbonate (25 mmol) and 0.29g of copper powder (4.6 mmol) were charged into a 100mL round bottom flask, followed by 50mL of o-dichlorobenzene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 190℃for 24 hours under closed conditions. After the reaction is completed, when the reaction system is cooled to room temperature, insoluble solid particles in the system are filtered and removed, and the obtained solution is subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: ethyl acetate=1:1 (volume ratio). The white solid obtained by column chromatography was 3.15g, and the yield was 74.3%.
3.15g (9.82 mmol) of the obtained intermediate, 2.22g (4.8 mmol) of 1, 4-dichloro-tetrabromobenzene, 0.14g (0.25 mmol) of bis-dibenzylideneacetone palladium, 0.15g (0.75 mmol) of tri-tert-butylphosphine, 4.89g (15 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=2:1 (volume ratio). The orange solid obtained by column chromatography was 2.54g and the yield was 68%.
2.54g (3.26 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 4.1mL (9.78 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5h at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2h. The temperature of the reaction system was lowered to-40℃and 0.93mL (9.78 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.67mL (15.65 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=5:1 (volume ratio). The purple solid obtained by column chromatography was 1.19g, and the yield was 50.2%. MALDI-TOF-MS results: molecular ion peak: 726.04. elemental analysis results: theoretical value: c,69.44; h,2.22; b,2.98; n,7.71; s,17.65. Experimental values: c,69.43; h,2.23; b,2.98; n,7.72; s,17.64.
Synthesis example 21: synthesis of Compound C67
This example is substantially identical to synthesis example 20, except that: in this case, the o-bromophenyl mercaptan is replaced by an equivalent amount of 5-trifluoromethyl-2-bromophenyl mercaptan. MALDI-TOF-MS results: molecular ion peak: 997.99. elemental analysis results: theoretical value: c,55.34; h,1.21; b,2.17; f,22.83; n,5.61; s,12.84. Experimental values: c,55.33; h,1.20; b,2.18; f,22.83; n,5.60; s,12.85.
Synthesis example 22: synthesis of Compound C70
This example is substantially identical to synthesis example 20, except that: in this case, the o-bromophenyl mercaptan is replaced by an equivalent amount of 5-isopropyl-2-bromophenyl mercaptan. MALDI-TOF-MS results: molecular ion peak: 894.23. elemental analysis results: theoretical value: c,72.48; h,4.51; b,2.42; n,6.26; s,14.33. Experimental values: c,72.49; h,4.51; b,2.43; n,6.25; s,14.32.
Synthesis example 23: synthesis of Compound C72
This example is substantially identical to synthesis example 20, except that: in this case, the o-bromophenyl mercaptan is replaced by an equivalent amount of 5-tert-butyl-2-bromophenyl mercaptan. MALDI-TOF-MS results: molecular ion peak: 950.29. elemental analysis results: theoretical value: c,73.26; h,5.09; b,2.27; n,5.89; s,13.49. Experimental values: c,73.28; h,5.10; b,2.27; n,5.88; s,13.48.
Synthesis example 24: synthesis of Compound C74
This example is substantially identical to synthesis example 20, except that: in this case, the o-bromophenyl mercaptan is replaced by an equivalent amount of 5-methyl-2-bromophenyl mercaptan. MALDI-TOF-MS results: molecular ion peak: 782.11. elemental analysis results: theoretical value: c,70.60; h,3.09; b,2.76; n,7.16; s,16.39. Experimental values: c,70.61; h,3.08; b,2.76; n,7.17; s,16.38.
Synthesis example 25: synthesis of Compound C76
This example is substantially identical to synthesis example 20, except that: in this case, the o-bromophenyl mercaptan is replaced by an equivalent amount of 5-methoxy-2-bromophenyl mercaptan. MALDI-TOF-MS results: molecular ion peak: 846.09. elemental analysis results: theoretical value: c,65.26; h,2.86; b,2.55; n,6.62; o,7.56; s,15.15. Experimental values: c,65.27; h,2.85; b,2.55; n,6.63; o,7.55; s,15.16.
Synthesis example 26: synthesis of Compound C78
This example is substantially identical to synthesis example 20, except that: in this case, the o-bromophenyl mercaptan is replaced with an equivalent amount of 4-bromo-3-mercaptopyridine. MALDI-TOF-MS results: molecular ion peak: 730.03. elemental analysis results: theoretical value: c,62.49; h,1.66; b,2.96; n,15.34; s,17.56. Experimental values: c,62.48; h,1.65; b,2.96; n,15.35; s,17.57.
Synthesis example 27: synthesis of Compound C83
In this synthesis example, compound C83 was synthesized according to the following scheme.
3.14g (9.8 mmol) of the Z3 intermediate, 3.78g (4.8 mmol) of the Z2 intermediate, 0.14g (0.25 mmol) of bis-dibenzylideneacetone palladium, 0.15g (0.75 mmol) of tri-tert-butylphosphine, 4.89g (15 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=1:2 (volume ratio). The orange solid obtained by column chromatography separation was 3.69g with a yield of 69.5%.
3.69g (3.34 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 4.2mL (10.02 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5h at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2h. The temperature of the reaction system was lowered to-40℃and 0.95mL (10.02 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.73mL (16.03 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=3:1 (volume ratio). The purple solid obtained by column chromatography was 1.55g, and the yield was 46.5%. MALDI-TOF-MS results: molecular ion peak: 998.12. elemental analysis results: theoretical value: c,72.18; h,2.22; b,4.33; n,8.42; s,12.85. Experimental values: c,72.17; h,2.22; b,4.32; n,8.43; s,12.86.
Synthesis example 28: synthesis of Compound C84
This example is substantially identical to synthesis example 27, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-methyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1026.15. elemental analysis results: theoretical value: c,72.55; h,2.55; b,4.21; n,8.19; s,12.49. Experimental values: c,72.56; h,2.55; b,4.22; n,8.18; s,12.48.
Synthesis example 29: synthesis of Compound C86
This example is substantially identical to synthesis example 27, except that: in this example, the raw material of O-bromobenzenethiol for synthesizing the Z3 intermediate and the raw material of 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate are required to be changed into 5-methyl-2-bromobenzenethiol and 4-methyl-2, 6-dichloro-1-bromobenzene in equal amounts. MALDI-TOF-MS results: molecular ion peak: 1082.21. elemental analysis results: theoretical value: c,73.23; h,3.17; b,3.99; n,7.76; s,11.85. Experimental values: c,73.22; h,3.17; b,3.98; n,7.77; s,11.84.
Synthesis example 30: synthesis of Compound C84
This example is substantially identical to synthesis example 27, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was replaced with an equal amount of 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1134.09. elemental analysis results: theoretical value: c,65.65; h,1.78; b,3.81; f,10.05; n,7.41; s,11.31. Experimental values: c,65.66; h,1.77; b,3.81; f,10.04; n,7.42; s,11.32.
Synthesis example 31: synthesis of Compound C86
This example is substantially identical to synthesis example 27, except that: in this example, the raw material of O-bromobenzenethiol for synthesizing the Z3 intermediate and the raw material of 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate are required to be changed into 5-trifluoromethyl-2-bromobenzenethiol and 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene in equal amounts. MALDI-TOF-MS results: molecular ion peak: 1406.04. elemental analysis results: theoretical value: c,56.37; h,1.15; b,3.07; f,24.32; n,5.98; s,9.12. Experimental values: c,56.38; h,1.15; b,3.06; f,24.31; n,5.97; s,9.13.
Synthesis example 32: synthesis of Compound C89
This example is substantially identical to synthesis example 27, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was converted to an equivalent amount of 4-isopropyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1082.21. elemental analysis results: theoretical value: c,73.23; h,3.17; b,3.99; n,7.76; s,11.85. Experimental values: c,73.22; h,3.17; b,3.98; n,7.77; s,11.86.
Synthesis example 33: synthesis of Compound C90
This example is substantially identical to synthesis example 27, except that: in this example, the raw materials of O-bromophenyl mercaptan for synthesizing the Z3 intermediate and 2, 6-dichloro-1-bromophenyl for synthesizing the Z2 intermediate were replaced with the same amounts of 5-isopropyl-2-bromophenyl mercaptan and 4-isopropyl-2, 6-dichloro-1-bromophenyl. MALDI-TOF-MS results: molecular ion peak: 1250.40. elemental analysis results: theoretical value: c,74.90; h,4.67; b,3.46; n,6.72; s,10.25. Experimental values: c,74.91; h,4.66; b,3.47; n,6.71; s,10.26.
Synthesis example 34: synthesis of Compound C92
This example is substantially identical to synthesis example 27, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-tert-butyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1110.24. elemental analysis results: theoretical value: c,73.54; h,3.45; b,3.89; n,7.57; s,11.55. Experimental values: c,73.55; h,3.44; b,3.87; n,7.58; s,11.56.
Synthesis example 35: synthesis of Compound C93
This example is substantially identical to synthesis example 27, except that: in this example, the raw materials of o-bromobenzenethiol and 2, 6-dichloro-1-bromobenzene are converted into 5-tert-butyl-2-bromobenzenethiol and 4-tert-butyl-2, 6-dichloro-1-bromobenzene in equal amounts. MALDI-TOF-MS results: molecular ion peak: 1334.49. elemental analysis results: theoretical value: c,75.57; h,5.29; b,3.24; n,6.30; s,9.61. Experimental values: c,75.56; h,5.29; b,3.23; n,6.31; s,9.62.
Synthesis example 36: synthesis of Compound C95
This example is substantially identical to synthesis example 27, except that: in this example, the raw materials of O-bromophenyl mercaptan for synthesizing the Z3 intermediate and 2, 6-dichloro-1-bromophenyl for synthesizing the Z2 intermediate are replaced by 5-methoxy-2-bromophenyl mercaptan and 4-methoxy-2, 6-dichloro-1-bromophenyl in equal amounts. MALDI-TOF-MS results: molecular ion peak: 1178.18. elemental analysis results: theoretical value: c,67.26; h,2.91; b,3.67; n,7.13; o,8.15; s,10.88. Experimental values: c,67.25; h,2.92; b,3.67; n,7.14; o,8.14; s,10.89.
Synthesis example 37: synthesis of Compound C101
This example is substantially identical to synthesis example 27, except that: in this example, the raw material o-bromophenyl mercaptan for the synthesis of the Z3 intermediate was replaced with an equivalent amount of 4-bromo-3 ',5' -bis (trifluoromethyl) - [1,1' -biphenyl ] -3-thiol. MALDI-TOF-MS results: molecular ion peak: 1846.14. elemental analysis results: theoretical value: c,59.84; h,1.64; b,2.34; f,24.69; n,4.55; s,6.94. Experimental values: c,59.83; h,1.65; b,2.35; f,24.68; n,4.54; s,6.95.
Synthesis example 38: synthesis of Compound C103
In this synthesis example, compound C103 was synthesized according to the following scheme.
3.30g (14 mmol) of o-dibromobenzene, 4.54g (30 mmol) of methyl 2-aminobenzoate, 0.16g (0.7 mmol) of palladium acetate, 0.42g (2.1 mmol) of tri-tert-butylphosphine, 13.68g (42 mmol) of cesium carbonate were charged into a 250mL three-necked flask, followed by 100mL of toluene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 36 hours under closed conditions. After the reaction was completed, the reaction was quenched with 200mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 200mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=1:1 (volume ratio). The yellow solid obtained by column chromatography was 4.12g and the yield was 78.2%.
To a dry two-necked flask, 1.85g of magnesium (76.65 mmol) and 25mL of dehydrated ether were added under a nitrogen atmosphere, the temperature of the system was lowered to 0℃and 5.03mL of methyl iodide (80.48 mmol) was added dropwise thereto. After the addition was completed, the temperature of the system was raised to room temperature and the reaction was stirred for 2 hours. Subsequently, the mixed solution was transferred through a cannula into a two-necked flask containing 4.12g (10.95 mmol) of the intermediate obtained in the previous step and 25mL of anhydrous tetrahydrofuran, and the reaction was stirred at room temperature overnight. After the reaction was completed, the reaction solution was poured into ice water, extracted with ethyl acetate and the organic phase was separated, dried over anhydrous magnesium sulfate, and then solid particles were removed by filtration, followed by spin-evaporation to remove the organic solvent. The oily liquid obtained after rotary evaporation was added to 50mL of 85% strength phosphoric acid, and the reaction was stirred at room temperature overnight. After the reaction was completed, the reaction solution was poured into ice water, extracted with ethyl acetate and the organic phase was separated, dried over anhydrous magnesium sulfate, and then solid particles were removed by filtration, followed by spin-evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=4:1 (volume ratio). The white solid obtained by column chromatography was 2.54g and the yield was 68.1%.
2.54g (7.46 mmol) of the intermediate obtained in the previous step, 1.67g (3.6 mmol) of 1, 4-dichloro-tetrabromobenzene, 0.14g (0.25 mmol) of bis-dibenzylideneacetone palladium, 0.15g (0.75 mmol) of tri-tert-butylphosphine, 4.89g (15 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=1:1 (volume ratio). The orange solid obtained by column chromatography was 2.56g and the yield was 78.4%.
2.56g (2.82 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 3.6mL (8.46 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5h at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2h. The temperature of the reaction system was lowered to-40℃and 0.81mL (8.46 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.31mL (13.54 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=6:1 (volume ratio). The purple solid obtained by column chromatography was 1.10g, and the yield was 50.8%. MALDI-TOF-MS results: molecular ion peak: 766.34. elemental analysis results: theoretical value: c,84.61; h,5.26; b,2.82; n,7.31. Experimental values: c,84.61; h,5.25; b,2.83; n,7.32.
Synthesis example 39: synthesis of Compound C106
This example is essentially the same as synthesis example 38, except that: in this case, methyl 2-aminobenzoate is converted into methyl 5-trifluoromethyl-2-aminobenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peak: 1038.29. elemental analysis results: theoretical value: c,67.08; h,3.49; b,2.08; f,21.95; n,5.39. Experimental values: c,67.09; h,3.48; b,2.07; f,21.96; n,5.38.
Synthesis example 40: synthesis of Compound C111
This example is essentially the same as synthesis example 38, except that: in this case, methyl 2-aminobenzoate is converted into methyl 5-isopropyl-2-aminobenzoate in an equivalent amount. MALDI-TOF-MS results: molecular ion peak: 934.53. elemental analysis results: theoretical value: c,84.79; h,6.90; b,2.31; n,5.99. Experimental values: c,84.78; h,6.91; b,2.32; n,5.98.
Synthesis example 41: synthesis of Compound C115
This example is essentially the same as synthesis example 38, except that: in this case, methyl 2-aminobenzoate is converted into an equivalent amount of methyl 5-tert-butyl-2-aminobenzoate. MALDI-TOF-MS results: molecular ion peak: 990.59. elemental analysis results: theoretical value: c,84.84; h,7.32; b,2.18; n,5.65. Experimental values: c,84.83; h,7.33; b,2.17; n,5.66.
Synthesis example 42: synthesis of Compound C118
This example is essentially the same as synthesis example 38, except that: in this case, methyl 2-aminobenzoate is converted into methyl 4-aminonicotinate in an equivalent amount. MALDI-TOF-MS results: molecular ion peak: 770.32. elemental analysis results: theoretical value: c,77.94; h,4.71; b,2.81; n,14.54. Experimental values: c,77.93; h,4.72; b,2.80; n,14.55.
Synthesis example 43: synthesis of Compound C125
In this synthesis example, compound C125 was synthesized according to the following scheme.
3.34g (9.8 mmol) of the Z4 intermediate, 3.78g (4.8 mmol) of the Z2 intermediate, 0.14g (0.25 mmol) of bis-dibenzylideneacetone palladium, 0.15g (0.75 mmol) of tri-tert-butylphosphine, 4.89g (15 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=1:2 (volume ratio). The orange solid obtained by column chromatography was 3.70g with a yield of 67.3%.
3.69g (3.23 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 4.1mL (9.69 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5 hours at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2 hours. The temperature of the reaction system was lowered to-40℃and 0.92mL (9.69 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.64mL (15.50 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=25:1 (volume ratio). Column chromatography gave 1.40g of a dark red solid with a yield of 41.8%. MALDI-TOF-MS results: molecular ion peak: 1038.42. elemental analysis results: theoretical value: c,83.28; h,4.47; b,4.16; n,8.09. Experimental values: c,83.29; h,4.48; b,4.15; n,8.08.
Synthesis example 44: synthesis of Compound C126
This example is substantially identical to synthesis example 43, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was replaced with an equal amount of 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1174.39. elemental analysis results: theoretical value: c,75.68; h,3.78; b,3.68; f,9.71; n,7.16. Experimental values: c,75.69; h,3.78; b,3.67; f,9.70; n,7.17.
Synthesis example 45: synthesis of Compound C128
This example is substantially identical to synthesis example 43, except that: in this example, methyl 2-aminobenzoate as a raw material for synthesizing a Z4 intermediate and 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing a Z2 intermediate were converted into 5-trifluoromethyl-2-aminobenzoate and 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene in the same amounts. MALDI-TOF-MS results: molecular ion peak: 1446.34. elemental analysis results: theoretical value: c,64.77; h,2.79; b,2.99; f,23.64; n,5.81. Experimental values: c,64.79; h,2.78; b,2.98; f,23.63; n,5.82.
Synthesis example 46: synthesis of Compound C131
This example is substantially identical to synthesis example 43, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was converted to an equivalent amount of 4-isopropyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1122.51. elemental analysis results: theoretical value: c,83.45; h,5.21; b,3.85; n,7.49. Experimental values: c,83.44; h,5.22; b,3.86; n,7.48.
Synthesis example 47: synthesis of Compound C132
This example is substantially identical to synthesis example 43, except that: in this example, methyl 2-aminobenzoate as a raw material for synthesizing a Z4 intermediate and 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing a Z2 intermediate were required to be replaced with 5-isopropyl-2-aminobenzoate and 4-isopropyl-2, 6-dichloro-1-bromobenzene in the same amounts. MALDI-TOF-MS results: molecular ion peak: 1290.70. elemental analysis results: theoretical value: c,83.74; h,6.40; b,3.35; n,6.51. Experimental values: c,83.73; h,6.40; b,3.36; n,6.52.
Synthesis example 48: synthesis of Compound C134
This example is substantially identical to synthesis example 43, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-tert-butyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1150.54. elemental analysis results: theoretical value: c,83.51; h,5.43; b,3.76; n,7.30. Experimental values: c,83.50; h,5.42; b,3.77; n,7.31.
Synthesis example 49: synthesis of Compound C135
This example is substantially identical to synthesis example 43, except that: in this example, methyl 2-aminobenzoate as a raw material for synthesizing a Z4 intermediate and 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing a Z2 intermediate were replaced with 5-tert-butyl-2-aminobenzoate and 4-tert-butyl-2, 6-dichloro-1-bromobenzene in the same amounts. MALDI-TOF-MS results: molecular ion peak: 1375.79. elemental analysis results: theoretical value: c,83.85; h,6.89; b,3.14; n,6.11. Experimental values: c,83.84; h,6.88; b,3.15; n,6.12.
Synthesis example 50: synthesis of Compound C137
This example is substantially identical to synthesis example 43, except that: in this example, methyl 2-aminobenzoate as a raw material for synthesizing the Z4 intermediate and 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing the Z2 intermediate are required to be replaced by 5-methoxy-2-aminobenzoate and 4-methoxy-2, 6-dichloro-1-bromobenzene in the same amount. MALDI-TOF-MS results: molecular ion peak: 1218.48. elemental analysis results: theoretical value: c,76.88; h,4.80; b,3.55; n,6.90; o,7.88. Experimental values: c,76.87; h,4.80; b,3.54; n,6.91; o,7.89.
Synthesis example 51: synthesis of Compound C145
This example is substantially identical to synthesis example 43, except that: in this example, the starting material methyl 2-aminobenzoate for the synthesis of the Z4 intermediate was converted to methyl 4-aminonicotinate in an equivalent amount. MALDI-TOF-MS results: molecular ion peak: 1042.40. elemental analysis results: theoretical value: c,78.35; h,4.06; b,4.15; n,13.44. Experimental values: c,78.34; h,4.07; b,4.14; n,13.45.
Synthesis example 52: synthesis of Compound C150
In this synthesis example, compound C150 was synthesized according to the following scheme.
1.50g (10.02 mmol) of 2-aminocyclohexanone hydrochloride and 5.79g (40.08 mmol) of phenylhydrazine hydrochloride were dissolved in a mixed solution of 45mL of glacial acetic acid and 15mL of trifluoroacetic acid, and the solution was charged into a 100mL three-necked flask. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 100℃for 36 hours under closed conditions. After the reaction was completed, 100mL of water was added to the reaction system after the reaction system had cooled to room temperature, and the precipitated solid was collected by filtration. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: ethyl acetate=5:1 (volume ratio). The white solid obtained by column chromatography was 2.38g, and the yield was 92.5%.
2.38g (9.27 mmol) of the intermediate obtained in the previous step, 1.67g (4.6 mmol) of 1, 4-dichloro-tetrabromobenzene, 0.16g (0.28 mmol) of bis-dibenzylideneacetone palladium, 0.17g (0.83 mmol) of tri-tert-butylphosphine, and 7.49g (23 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=1:1 (volume ratio). The orange solid obtained by column chromatography separation was 2.12g with a yield of 70.6%.
2.12g (3.25 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the system to be reacted was lowered to 0℃and 4.1mL (9.75 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5 hours at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2 hours. The temperature of the reaction system was lowered to-40℃and 0.93mL (9.75 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.66mL (15.6 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=30:1 (volume ratio). The purple-black solid obtained by column chromatography separation was 0.94g, and the yield was 48.4%. MALDI-TOF-MS results: molecular ion peak: 598.16. elemental analysis results: theoretical value: c,84.32; h,2.70; b,3.61; n,9.37. Experimental values: c,84.31; h,2.71; b,3.62; n,9.36.
Synthesis example 53: synthesis of Compound C151
This embodiment is substantially the same as synthesis embodiment 52, except that: in this case, the phenylhydrazine hydrochloride is replaced by an equivalent amount of 4-methylphenylhydrazine hydrochloride. MALDI-TOF-MS results: molecular ion peak: 654.22. elemental analysis results: theoretical value: c,84.44; h,3.70; b,3.30; n,8.56. Experimental values: c,84.43; h,3.71; b,3.31; n,8.55.
Synthesis example 54: synthesis of Compound C152
This embodiment is substantially the same as synthesis embodiment 52, except that: in this case, the phenylhydrazine hydrochloride is replaced by an equivalent amount of 4-trifluoromethyl phenylhydrazine hydrochloride. MALDI-TOF-MS results: molecular ion peak: 870.11. elemental analysis results: theoretical value: c,63.49; h,1.39; b,2.48; f,26.20; n,6.44. Experimental values: c,63.48; h,1.39; b,2.47; f,26.21; n,6.45.
Synthesis example 55: synthesis of Compound C155
This embodiment is substantially the same as synthesis embodiment 52, except that: in this case, the phenylhydrazine hydrochloride is replaced by an equivalent amount of 4-isopropylphenylhydrazine hydrochloride. MALDI-TOF-MS results: molecular ion peak: 766.34. elemental analysis results: theoretical value: c,84.61; h,5.26; b,2.82; n,7.31. Experimental values: c,84.60; h,5.27; b,2.81; n,7.32.
Synthesis example 56: synthesis of Compound C157
This embodiment is substantially the same as synthesis embodiment 52, except that: in this case, the phenylhydrazine hydrochloride is replaced by an equivalent amount of 4-tert-butylphenyl hydrazine hydrochloride. MALDI-TOF-MS results: molecular ion peak: 822.41. elemental analysis results: theoretical value: c,84.68; h,5.88; b,2.63; n,6.81. Experimental values: c,84.67; h,5.89; b,2.64; n,6.80.
Synthesis example 57: synthesis of Compound C159
This embodiment is substantially the same as synthesis embodiment 52, except that: in this case, the phenylhydrazine hydrochloride is replaced by an equivalent amount of 4-methoxyphenylhydrazine hydrochloride. MALDI-TOF-MS results: molecular ion peak: 718.20. elemental analysis results: theoretical value: c,76.91; h,3.37; b,3.01; n,7.80; o,8.91. Experimental values: c,76.91; h,3.36; b,3.00; n,7.81; o,8.92.
Synthesis example 58: synthesis of Compound C160
In this synthesis example, compound C160 was synthesized according to the following scheme.
2.38g (9.27 mmol) of the Z5 intermediate, 3.62g (4.6 mmol) of the Z2 intermediate, 0.16g (0.28 mmol) of bis-dibenzylideneacetone palladium, 0.17g (0.83 mmol) of tri-tert-butylphosphine, and 7.49g (23 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=1:2 (volume ratio). The orange solid obtained by column chromatography was 3.08g with a yield of 68.5%.
3.08g (3.15 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 4.0mL (9.45 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5 hours at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2 hours. The temperature of the reaction system was lowered to-40℃and 0.90mL (9.45 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.57mL (15.12 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=35:1 (volume ratio). The dark purple black solid obtained by column chromatography separation is 1.20g, and the yield is 43.6%. MALDI-TOF-MS results: molecular ion peak: 870.12. elemental analysis results: theoretical value: c,82.82; h,2.55; b,4.97; n,9.66. Experimental values: c,82.83; h,2.54; b,4.96; n,9.67.
Synthesis example 59: synthesis of Compound C161
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-methyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 898.26. elemental analysis results: theoretical value: c,82.91; h,2.92; b,4.81; n,9.36. Experimental values: c,82.90; h,2.91; b,4.82; n,9.37.
Synthesis example 60: synthesis of Compound C163
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, the raw material phenylhydrazine hydrochloride for synthesizing the Z5 intermediate and the raw material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate are replaced by the same amount of 4-methylphenylhydrazine hydrochloride and 4-methyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 954.32. elemental analysis results: theoretical value: c,83.07; h,3.59; b,4.53; n,8.81. Experimental values: c,83.07; h,3.58; b,4.52; n,8.82.
Synthesis example 61: synthesis of Compound C164
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was replaced with an equal amount of 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1006.20. elemental analysis results: theoretical value: c,74.02; h,2.00; b,4.30; f,11.33; n,8.35. Experimental values: c,74.01; h,2.01; b,4.30; f,11.32; n,8.36.
Synthesis example 62: synthesis of Compound C166
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, raw material phenylhydrazine hydrochloride for synthesizing Z5 intermediate and raw material 2, 6-dichloro-1-bromobenzene for synthesizing Z2 intermediate are changed into equal amounts of 4-trifluoromethyl phenylhydrazine hydrochloride and 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1278.15. elemental analysis results: theoretical value: c,62.02; h,1.26; b,3.38; f,26.76; n,6.58. Experimental values: c,62.01; h,1.26; b,3.39; f,26.75; n,6.59.
Synthesis example 63: synthesis of Compound C167
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was converted to an equivalent amount of 4-isopropyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 954.32. elemental analysis results: theoretical value: c,83.07; h,3.59; b,4.53; n,8.81. Experimental values: c,83.06; h,3.58; b,4.54; n,8.82.
Synthesis example 64: synthesis of Compound C169
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, the raw material phenylhydrazine hydrochloride for synthesizing the Z5 intermediate and the raw material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate are changed into the same amount of 4-isopropylphenylhydrazine hydrochloride and 4-isopropyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1122.51. elemental analysis results: theoretical value: c,83.45; h,5.21; b,3.85; n,7.49. Experimental values: c,83.46; h,5.20; b,3.86; n,7.48.
Synthesis example 65: synthesis of Compound C170
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-tert-butyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 982.35. elemental analysis results: theoretical value: c,83.14; h,3.90; b,4.40; n,8.56. Experimental values: c,83.13; h,3.90; b,4.41; n,8.57.
Synthesis example 66: synthesis of Compound C172
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, the raw material phenylhydrazine hydrochloride for synthesizing the Z5 intermediate and the raw material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate are replaced by the same amount of 4-tert-butylphenylhydrazine hydrochloride and 4-tert-butyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1206.60. elemental analysis results: theoretical value: c,83.61; h,5.85; b,3.58; n,6.96. Experimental values: c,83.60; h,5.86; b,3.57; n,6.97.
Synthesis example 67: synthesis of Compound C173
This embodiment is substantially the same as synthesis embodiment 58, except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was replaced with an equal amount of 4-methoxy-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 930.25. elemental analysis results: theoretical value: c,80.06; h,2.82; b,4.65; n,9.04; o,3.44. Experimental values: c,80.05; h,2.82; b,4.64; n,9.05; o,3.45.
Synthesis example 68: synthesis of Compound C180
In this synthesis example, compound C180 was synthesized according to the following scheme.
2.36g (10 mmol) of o-dibromobenzene, 2.79g (30 mmol) of aniline, 0.06g (0.266 mmol) of palladium acetate, 0.162g (0.8 mmol) of tri-tert-butylphosphine, 2.883g (30 mmol) of sodium tert-butoxide were charged into a 100mL three-necked flask, followed by 50mL of toluene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=3:1 (volume ratio). The white green solid obtained by column chromatography was 2.15g, and the yield was 82.6%.
2.15g (8.26 mmol) of the intermediate obtained in the previous step, 1.49g (4.1 mmol) of 1, 4-dichloro-tetrabromobenzene, 0.14g (0.25 mmol) of bis-dibenzylideneacetone palladium, 0.15g (0.74 mmol) of tri-tert-butylphosphine, 6.68g (20.54 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=1:1 (volume ratio). The yellow solid obtained by column chromatography was 1.98g, and the yield was 73.1%.
1.98g (3 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the system to be reacted was lowered to 0℃and 3.8mL (9 mmol) of n-butyllithium pentane solution was slowly added thereto, stirring was carried out at 0℃for 0.5 hours, and then the temperature of the reaction system was raised to 60℃and stirring was continued for 2 hours. The temperature of the reaction system was lowered to-40℃and 0.84mL (9 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.46mL (14.4 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=20:1 (volume ratio). The purple solid obtained by column chromatography was 0.84g and the yield was 46.2%. MALDI-TOF-MS results: molecular ion peak: 606.22. elemental analysis results: theoretical value: c,83.20; h,3.99; b,3.57; n,9.24. Experimental values: c,83.21; h,3.98; b,3.56; n,9.26.
Synthesis example 69: synthesis of Compound C182
This example is substantially identical to synthesis example 68, except that: in this case, the aniline is replaced by an equivalent amount of 4-trifluoromethylaniline. MALDI-TOF-MS results: molecular ion peak: 878.17. elemental analysis results: theoretical value: c,62.91; h,2.30; b,2.46; f,25.96; n,6.38. Experimental values: c,62.92; h,2.31; b,2.45; f,25.95; n,6.39.
Synthesis example 70: synthesis of Compound C188
This example is substantially identical to synthesis example 68, except that: in this case, the aniline is replaced by an equal amount of 4-isopropylaniline. MALDI-TOF-MS results: molecular ion peak: 774.41. elemental analysis results: theoretical value: c,83.73; h,6.25; b,2.79; n,7.23. Experimental values: c,83.72; h,6.26; b,2.78; n,7.24.
Synthesis example 71: synthesis of Compound C192
This example is substantially identical to synthesis example 68, except that: in this case, the aniline is replaced by an equivalent amount of 4-t-butylaniline. MALDI-TOF-MS results: molecular ion peak: 830.47. elemental analysis results: theoretical value: c,83.86; h,6.79; b,2.60; n,6.74. Experimental values: c,83.87; h,6.78; b,2.61; n,6.73.
Synthesis example 72: synthesis of Compound C195
This example is substantially identical to synthesis example 68, except that: in this case, the aniline is replaced by an equivalent amount of 4-methylaniline. MALDI-TOF-MS results: molecular ion peak: 662.28. elemental analysis results: theoretical value: c,83.41; h,4.87; b,3.26; n,8.46. Experimental values: c,83.40; h,4.86; b,3.27; n,8.47.
Synthesis example 73: synthesis of Compound C197
This example is substantially identical to synthesis example 68, except that: in this case, the aniline is replaced by an equivalent amount of 4-methoxyaniline. MALDI-TOF-MS results: molecular ion peak: 726.26. elemental analysis results: theoretical value: c,76.06; h,4.44; b,2.98; n,7.71; o,8.81. Experimental values: c,76.05; h,4.44; b,2.99; n,7.70; o,8.82.
Synthesis example 74: synthesis of Compound C202
This example is substantially identical to synthesis example 68, except that: in this case, aniline is replaced by an equivalent amount of 4-aminopyridine. MALDI-TOF-MS results: molecular ion peak: 610.20. elemental analysis results: theoretical value: c,74.79; h,3.30; b,3.54; n,18.36. Experimental values: c,74.78; h,3.29; b,3.55; n,18.37.
Synthesis example 75: synthesis of Compound C209
This example is substantially identical to synthesis example 68, except that: in this case, the o-dibromobenzene is replaced by an equivalent amount of 4, 5-bis (trifluoromethyl) -1, 2-dibromobenzene. MALDI-TOF-MS results: molecular ion peak: 878.17. elemental analysis results: theoretical value: c,62.91; h,2.30; b,2.46; f,25.96; n,6.38. Experimental values: c,62.92; h,2.30; b,2.45; f,25.95; n,6.39.
Synthesis example 76: synthesis of Compound C212
In this synthesis example, compound C212 was synthesized according to the following scheme.
2.41g (9.27 mmol) of the Z6 intermediate, 3.62g (4.6 mmol) of the Z2 intermediate, 0.16g (0.28 mmol) of bis-dibenzylideneacetone palladium, 0.17g (0.83 mmol) of tri-tert-butylphosphine, and 7.49g (23 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=1:2 (volume ratio). The orange-yellow solid obtained by column chromatography was 3.26g and the yield was 71.9%.
3.26g (3.31 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 4.2mL (9.93 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5h at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2h. The temperature of the reaction system was lowered to-40℃and 0.95mL (9.93 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.7mL (15.89 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=35:1 (volume ratio). The dark purple black solid obtained by column chromatography separation is 1.31g, and the yield is 45.1%. MALDI-TOF-MS results: molecular ion peak: 878.29. elemental analysis results: theoretical value: c,82.06; h,3.44; b,4.92; n,9.57. Experimental values: c,82.07; h,3.43; b,4.91; n,9.58.
Synthesis example 77: synthesis of Compound C213
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-methyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 906.32. elemental analysis results: theoretical value: c,82.17; h,3.78; b,4.77; n,9.27. Experimental values: c,82.16; h,3.77; b,4.78; n,9.28.
Synthesis example 78: synthesis of Compound C215
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the aniline as a raw material for synthesizing the Z6 intermediate and the 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing the Z2 intermediate were replaced with the 4-methylaniline and 4-methyl-2, 6-dichloro-1-bromobenzene in the same amounts. MALDI-TOF-MS results: molecular ion peak: 962.38. elemental analysis results: theoretical value: c,82.37; h,4.40; b,4.49; n,8.73. Experimental values: c,82.36; h,4.41; b,4.48; n,8.74.
Synthesis example 79: synthesis of Compound C219
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was replaced with an equal amount of 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 1014.27. elemental analysis results: theoretical value: c,73.43; h,2.78; b,4.26; f,11.24; n,8.29. Experimental values: c,73.44; h,2.78; b,4.25; f,11.25; n,8.28.
Synthesis example 80: synthesis of Compound C221
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the aniline as a raw material for synthesizing the Z6 intermediate and the 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing the Z2 intermediate were replaced with the 4-trifluoromethylaniline and 4-trifluoromethyl-2, 6-dichloro-1-bromobenzene in the same amounts. MALDI-TOF-MS results: molecular ion peak: 1286.21. elemental analysis results: theoretical value: c,61.63; h,1.88; b,3.36; f,26.59; n,6.53. Experimental values: c,61.64; h,1.88; b,3.35; f,26.58; n,6.54.
Synthesis example 81: synthesis of Compound C225
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was converted to an equivalent amount of 4-isopropyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 962.38. elemental analysis results: theoretical value: c,82.37; h,4.40; b,4.49; n,8.73. Experimental values: c,82.36; h,4.41; b,4.48; n,8.74.
Synthesis example 82: synthesis of Compound C227
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, aniline as a raw material for synthesizing the Z6 intermediate and 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing the Z2 intermediate were replaced with 4-isopropylaniline and 4-isopropyl-2, 6-dichloro-1-bromobenzene in the same amounts. MALDI-TOF-MS results: molecular ion peak: 1130.57. elemental analysis results: theoretical value: c,82.86; h,5.88; b,3.82; n,7.43. Experimental values: c,82.85; h,5.89; b,3.81; n,7.44.
Synthesis example 83: synthesis of Compound C230
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for the synthesis of the Z2 intermediate was replaced with an equivalent amount of 4-tert-butyl-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 990.42. elemental analysis results: theoretical value: c,82.47; h,4.68; b,4.37; n,8.49. Experimental values: c,82.46; h,4.69; b,4.38; n,8.48.
Synthesis example 85: synthesis of Compound C232
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the aniline as a raw material for synthesizing the Z6 intermediate and the 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing the Z2 intermediate were replaced with 4-tert-butylaniline and 4-tert-butyl-2, 6-dichloro-1-bromobenzene in the same amounts. MALDI-TOF-MS results: molecular ion peak: 1214.67. elemental analysis results: theoretical value: c,83.05; h,6.47; b,3.56; n,6.92. Experimental values: c,83.04; h,6.48; b,3.55; n,6.93.
Synthesis example 86: synthesis of Compound C235
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the starting material 2, 6-dichloro-1-bromobenzene for synthesizing the Z2 intermediate was replaced with an equal amount of 4-methoxy-2, 6-dichloro-1-bromobenzene. MALDI-TOF-MS results: molecular ion peak: 938.31. elemental analysis results: theoretical value: c,79.37; h,3.65; b,4.61; n,8.96; o,3.41. Experimental values: c,79.36; h,3.65; b,4.62; n,8.95; o,3.42.
Synthesis example 87: synthesis of Compound C238
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the aniline as a raw material for synthesizing the Z6 intermediate and the 2, 6-dichloro-1-bromobenzene as a raw material for synthesizing the Z2 intermediate were replaced with the 4-methoxyaniline and 4-methoxy-2, 6-dichloro-1-bromobenzene in the same amounts. MALDI-TOF-MS results: molecular ion peak: 1058.35. elemental analysis results: theoretical value: c,74.90; h,4.00; b,4.09; n,7.94; o,9.07. Experimental values: c,74.88; h,4.01; b,4.08; n,7.95; o,9.08.
Synthesis example 88: synthesis of Compound C257
This embodiment is substantially the same as synthesis embodiment 76 except that: in this example, the raw material o-dibromobenzene for synthesizing the Z6 intermediate was replaced with an equal amount of 4, 5-bis (trifluoromethyl) -1, 2-dibromobenzene. MALDI-TOF-MS results: molecular ion peak: 1150.24. elemental analysis results: theoretical value: c,66.83; h,2.28; b,3.76; f,19.82; n,7.31. Experimental values: c,66.82; h,2.28; b,3.77; f,19.81; n,7.32.
Synthesis example 89: synthesis of Compound C264
In this synthesis example, compound C264 was synthesized according to the following scheme.
10H-phenoxazine 13.95g (70 mmol), lithium bromide 24.32g (280 mmol) and boron trifluoride etherate 19.87g (140 mmol) were added to a 500mL three-necked flask followed by 300mL dimethylsulfoxide. An oxygen balloon device was placed on one side of the three-necked flask, and the reaction was carried out overnight at room temperature. After the reaction was completed, a large amount of deionized water was added to the reaction system, and the organic phase was extracted with ethyl acetate several times and separated. The collected organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=5:1 (volume ratio). The pale yellow powdery solid obtained by column chromatography was 13.23g, and the yield was 72.1%.
13.23g (50.47 mmol) of the intermediate obtained in the previous step was dissolved in 150mL of anhydrous pyridine solution and placed in a three-necked flask, to which 44.07g (201.88 mmol) of di-tert-butyl dicarbonate was added. The gas in the three-necked flask was replaced with nitrogen, followed by stirring at 80℃for 24 hours under closed conditions. After the reaction was completed, 200mL of water was added to the reaction system after the reaction system was cooled to room temperature, and the organic phase was extracted with ethyl acetate several times and separated. The collected organic phase was dried over anhydrous sodium sulfate, filtered to remove solid particles, and then subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=3:1 (volume ratio). The pale yellow solid obtained by column chromatography separation was 15.98g, and the yield was 87.4%.
15.98g (44.11 mmol) of the intermediate obtained in the previous step, 6.67g (44.11 mmol) of methyl anthranilate, 12.20g (88.22 mmol) of potassium carbonate, 1.52g (13.23 mmol) of L-proline and 2.52g (13.23 mmol) of cuprous iodide were charged into a 250mL three-necked flask, followed by 100mL of 2-pentanol. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 130℃for 24 hours under closed conditions. After the reaction was completed, 200mL of water was added to the reaction system after the reaction system was cooled to room temperature, and the insoluble impurities were removed by suction filtration. The resulting clear solution was acidified to ph=2 with 2M hydrochloric acid, then ethyl acetate was added thereto, and the organic phase was extracted and separated multiple times. The collected organic phase was dried over anhydrous sodium sulfate, and solid particles were removed by filtration, followed by spin-evaporation to remove the organic solvent, to give 13.37g of a white solid product in a yield of 70.1%.
13.37g (30.92 mmol) of the intermediate obtained in the previous step and 100mL of methylene chloride were added to a 250mL round bottom flask, 15mL of trifluoroacetic acid was slowly added dropwise thereto under stirring, and after the addition was completed, the reaction was stirred at room temperature, and TLC was used to monitor the progress of the reaction until the reaction was completed. The organic solvent is removed by rotary evaporation in the reaction system, the obtained crude product is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=5:1 (volume ratio). The pale yellow white powdery solid obtained by column chromatography was 7.45g, and the yield was 72.5%.
To a dry two-necked flask, 3.70g of magnesium (153.3 mmol) and 50mL of dehydrated ether were added under a nitrogen atmosphere, the temperature of the system was lowered to 0℃and 10.06mL of methyl iodide (160.96 mmol) was added dropwise thereto. After the addition was completed, the temperature of the system was raised to room temperature and the reaction was stirred for 4 hours. Subsequently, the mixed solution was transferred through a cannula into a two-necked flask containing 7.45g (22.42 mmol) of the intermediate obtained in the previous step and 100mL of anhydrous tetrahydrofuran, and the reaction was stirred at room temperature overnight. After the reaction was completed, the reaction solution was poured into ice water, extracted with ethyl acetate and the organic phase was separated, dried over anhydrous magnesium sulfate, and then solid particles were removed by filtration, followed by spin-evaporation to remove the organic solvent. The oily liquid obtained after rotary evaporation was added to 50mL of 85% strength phosphoric acid, and the reaction was stirred at room temperature overnight. After the reaction was completed, the reaction solution was poured into ice water, extracted with ethyl acetate and the organic phase was separated, dried over anhydrous magnesium sulfate, and then solid particles were removed by filtration, followed by spin-evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the mixture ratio are n-hexane: dichloromethane=4:1 (volume ratio). The white solid obtained by column chromatography was 4.39g and the yield was 62.3%.
4.39g (13.97 mmol) of the intermediate obtained in the previous step, 2.47g (6.8 mmol) of 1, 4-dichloro-tetrabromobenzene, 0.23g (0.41 mmol) of bis-dibenzylideneacetone palladium, 0.25g (1.23 mmol) of tri-tert-butylphosphine, 11.08g (34.06 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=2:1 (volume ratio). The yellow solid obtained by column chromatography was 3.65g with a yield of 69.9%.
3.65g (4.75 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the system to be reacted was lowered to 0℃and 6.02mL (14.25 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5h at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2h. The temperature of the reaction system was lowered to-40℃and 1.33mL (14.25 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 3.9mL (22.8 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=25:1 (volume ratio). The purple solid obtained by column chromatography was 1.64g and the yield was 48.2%. MALDI-TOF-MS results: molecular ion peak: 714.24. elemental analysis results: theoretical value: c,80.70; h,3.95; b,3.03; n,7.84; o,4.48. Experimental values: c,80.70; h,3.94; b,3.02; n,7.85; o,4.49.
Synthesis example 90: synthesis of Compound C265
This example is substantially identical to synthesis example 89, except that: in this case, 10H-phenoxazine is replaced by an equivalent amount of 10H-phenothiazine. MALDI-TOF-MS results: molecular ion peak: 746.19. elemental analysis results: theoretical value: c,77.23; h,3.78; b,2.90; n,7.51; s,8.59. Experimental values: c,77.24; h,3.78; b,2.91; n,7.52; s,8.58.
Synthesis example 91: synthesis of Compound C291
In this synthesis example, compound C291 was synthesized according to the following scheme.
2.91g (9.27 mmol) of the Z7 intermediate, 3.62g (4.6 mmol) of the Z2 intermediate, 0.16g (0.28 mmol) of bis-dibenzylideneacetone palladium, 0.17g (0.83 mmol) of tri-tert-butylphosphine, and 7.49g (23 mmol) of cesium carbonate were charged into a 100mL three-necked flask, followed by 50mL of o-xylene. The gas in the three-necked flask was replaced with nitrogen, followed by stirring under reflux at 120℃for 24 hours under closed conditions. After the reaction was completed, the reaction was quenched with 100mL of ammonium chloride solution when the reaction system was cooled to room temperature. To this solution was added 100mL of methylene chloride, and the organic phase was extracted and separated. The aqueous phase system was further extracted with dichloromethane, the resulting organic phases were collected and combined, dried over anhydrous sodium sulfate, filtered to remove solid particles, and subsequently subjected to rotary evaporation to remove the organic solvent. The crude product obtained is subjected to column chromatography separation, and the eluent and the proportion used are petroleum ether: dichloromethane=1:1 (volume ratio). The orange-yellow solid obtained by column chromatography was 3.46g and the yield was 68.8%.
3.46g (3.16 mmol) of the intermediate obtained in the previous step was dissolved in 25mL of t-butylbenzene under nitrogen protection, the temperature of the reaction system was lowered to 0℃and 4.0mL (9.48 mmol) of n-butyllithium pentane solution was slowly added thereto, and stirring was continued for 0.5 hours at 0℃followed by raising the temperature of the reaction system to 60℃and continuing stirring for 2 hours. The temperature of the reaction system was lowered to-40℃and 0.91mL (9.48 mmol) of boron tribromide was added thereto at this temperature, followed by raising the temperature of the reaction system to room temperature and stirring for 0.5h. The temperature of the reaction system was lowered to 0℃and 2.6mL (15.17 mmol) of N, N-diisopropylethylamine was added thereto. The reaction temperature was then raised to 120℃and allowed to react for 5h with stirring. After the reaction is completed, when the reaction system is cooled to room temperature, the reaction system is poured into a mixed solution of sodium acetate aqueous solution and dichloromethane, an organic layer is obtained by extracting and separating the liquid, then the aqueous phase is extracted twice, the obtained organic phases are combined, dried by anhydrous sodium sulfate, solid particles are filtered, and then the organic solvent is removed by rotary evaporation. The crude product obtained is subjected to column chromatography separation, and the eluent used and the proportion are methylene dichloride: petroleum ether=35:1 (volume ratio). The dark purple black solid obtained by column chromatography separation is 1.44g, and the yield is 46.3%. MALDI-TOF-MS results: molecular ion peak: 986.31. elemental analysis results: theoretical value: c,80.38; h,3.47; b,4.38; n,8.52; o,3.24. Experimental values: c,80.39; h,3.46; b,4.37; n,8.51; o,3.25.
Synthesis example 92: synthesis of Compound C292
This example is substantially identical to synthesis example 91, except that: in this example, the starting material 10H-phenoxazine for the synthesis of the Z7 intermediate was replaced with an equivalent amount of 10H-phenothiazine. MALDI-TOF-MS results: molecular ion peak: 1018.27. elemental analysis results: theoretical value: c,77.84; h,3.37; b,4.25; n,8.25; s,6.30. Experimental values: c,77.83; h,3.38; b,4.24; n,8.24; s,6.31.
Application embodiments of the compounds prepared according to the invention:
the compounds of the invention can be used in organic electroluminescent devices, i.e. OLED devices, most preferably as materials in the light-emitting layer.
The OLED includes a first electrode and a second electrode, and an organic material layer between the electrodes. The organic material may in turn be divided into a plurality of regions. For example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
In particular embodiments, a substrate may be used below the first electrode or above the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance and transparency. A Thin Film Transistor (TFT) may be provided on a substrate for a display.
The first electrode may be formed by sputtering or depositing a material serving as the first electrode on the substrate. When the first electrode is used as the anode, indium Tin Oxide (ITO), indium Zinc Oxide (IZO), tin dioxide (SnO) 2 ) An oxide transparent conductive material such as zinc oxide (ZnO), and any combination thereof. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) and any combination thereof can be used.
The organic material layer may be formed on the electrode by vacuum thermal evaporation, spin coating, ink jet printing, or the like. The compounds used as the organic material layer may be small organic molecules, large organic molecules and polymers, and combinations thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer hole transport layer containing only one compound and a single layer hole transport layer containing a plurality of compounds. The hole transport region may have a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or conductive dopant containing polymers such as polystyrene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives.
The hole injection layer is positioned between the anode and the hole transport layer, and the hole injection layer can be made of a single compound material or a combination of multiple compounds.
The light-emitting layer material used in the organic electroluminescent device of the present invention is selected from one of the preferred compounds C1 to C303 of the present invention.
The OLED organic material layer may further include an electron transport region between the light emitting layer and the cathode. The electron transport region may be an Electron Transport Layer (ETL) of a single layer structure including a single layer electron transport layer containing only one compound and a single layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
The device may further include an electron injection layer between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, a combination of one or more of the following: liq, liF, naCl, csF, li 2 O,Cs 2 CO 3 ,BaO,Na,Li,Ca。
The technical effects and advantages of the present invention are demonstrated and verified by testing the practical use properties by specifically applying the compounds of the present invention to an organic electroluminescent device.
The preparation process of the organic electroluminescent device comprises the following steps:
the glass plate coated with the ITO transparent conductive layer was sonicated in commercial cleaners, rinsed in deionized water, and rinsed in acetone: ultrasonic degreasing in isopropanol mixed solvent, baking in clean environment to completely remove water, cleaning with ultraviolet light and ozone, and bombarding the surface with low-energy cation beam;
placing the above glass substrate with anode in vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, vacuum evaporating a hole injection layer on the anode layer film, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 5-10 nm; vacuum evaporating a hole transport layer on the hole injection layer, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 60-80 nm; vacuum vapor plating a light-emitting layer of a device on a hole transport layer, wherein the light-emitting layer of the invention comprises a host material and a dye material, wherein the dye material is selected from the group consisting of the compounds C1, C4, C9, C13, C32, C40, C45, C50, C65, C67, C70, C72, C83, C86, C90, C93, C103, C106, C111, C115, C125, C128, C132, C135, C150, C152, C155, C157, C160, C166, C169, C172, C180, C182, C188, C192, C212, C221, C227, C232, And C265 and C292, wherein the evaporation rate of the main material is regulated to be 0.1nm/s, the evaporation rate of the dye in the light-emitting layer is regulated to be 3% proportion, and the total film thickness of the light-emitting layer in evaporation is regulated to be 30nm. Vacuum evaporating an electron transport layer material of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30-60 nm; liF with the thickness of 1nm is vacuum evaporated on an Electron Transport Layer (ETL) to serve as an electron injection layer, and an Al layer with the thickness of 150nm serves as a cathode of the device.
The OLED device is tested in an integrating sphere under room temperature and atmospheric conditions, and parameters such as voltage, external quantum efficiency, current density and brightness of the device can be measured through an absolute external quantum efficiency measuring system C9920-12 of the Japanese Korea pine (Hamamatsu) company, a equipped Korea pine C10027-02 type PMA-12 photon multichannel spectrometer (detection range is 350-1100 nm) and a multifunctional power supply ammeter Keithley 2400.
The following devices OLED1 through OLED42 using the compounds of this invention C1, C4, C9, C13, C32, C40, C45, C50, C65, C67, C70, C72, C83, C86, C90, C93, C103, C106, C111, C115, C125, C128, C132, C135, C150, C152, C155, C157, C160, C166, C169, C172, C180, C182, C188, C192, C212, C221, C227, C232, C265 and C292 were prepared according to the procedure described above.
The film thickness of each OLED device structure and each layer is shown below:
inventive device example 1:
using the compound C1 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C1: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 2:
using the compound C4 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C4: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 3:
using the compound C9 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C9: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 4:
using the compound C13 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C13: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 5:
using the compound C32 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C32: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 6:
using the compound C40 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C40: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 7:
using the compound C45 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C45: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 8:
using the compound C50 of the present invention as a light emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C50:mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 9:
using the compound C65 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C65: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Device example 10 of the present invention:
using the compound C67 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C67: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 11:
using the compound C70 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C70: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 12:
using the compound C72 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C72: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 13:
using the compound C83 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C83: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 14:
using the compound C86 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C86: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 15:
using the compound C90 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C90: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 16:
using the compound C93 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C93: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 17:
using the compound C103 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C103: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 18:
using the compound C106 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C106: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 19:
using the compound C111 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C111: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 20:
using the compound C115 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C115: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 21:
using the compound C125 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C125: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 22:
using the compound C128 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C128: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 23:
using the compound C132 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C132: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 24:
using the compound C135 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C135: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 25:
using the compound C150 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C150: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 26:
using the compound C152 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C152: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 27:
using the compound C155 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C155: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 28:
using the compound C157 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C157: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the above organic electroluminescent device test method.
Inventive device example 29:
using the compound C160 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C160: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 30:
using the compound C166 of the present invention as a light emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C166: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 31:
using the compound C169 of the present invention as a light-emitting material, the device structure was: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C169: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 32:
using the compound C172 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C172: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 33:
using the compound C180 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C180: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 34:
using the compound C182 of the present invention as a light emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C182: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 35:
using the compound C188 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C188:mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 36:
using the compound C192 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C192: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 37:
using the compound C212 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C212: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 38:
using the compound C221 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C221: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 39:
using the compound C227 of the present invention as a light-emitting material, the device structure was: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C227: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 40:
using the compound C232 of the present invention as a light-emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C232: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 41:
using the compound C265 of the present invention as a light emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C265: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Inventive device example 42:
using the compound C292 of the present invention as a light-emitting material, the device structure was: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% C292: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Comparative device example 1:
using the compound DABA-1 of the prior art as a luminescent material, the device structure is: ITO/NPD (40 nm)/TCTA (15 nm)/1 wt% DABCNA-1:mCBP (20 nm)/TSPO 1 (40 nm)/LiF (1 nm)/Al (100 nm), and performing device performance test according to the organic electroluminescent device test method.
Comparative device example 2:
using the compound R-BN of the prior art as a luminescent material, the device structure is: ITO/HATCN (10 nm)/TAPC (60 nm)/TCTA (10 nm)/CBP 30wt% Ir (mphmq) 2tmd 3wt% R-BN (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (0.5 nm)/Al (150 nm) device performance was tested according to the organic electroluminescent device test method described above.
Comparative device example 3:
using prior art compounds 1-423 as light emitting materials, the device structure was: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt%1-423: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm), and performing device performance test according to the organic electroluminescent device test method.
Comparative device example 4:
using the compound D1 of the prior art as a light emitting material, the device structure is: ITO/HATCN (10 nm)/TAPC (50 nm)/TCTA (10 nm)/3 wt% D1: mCBP (30 nm)/CzPhPy (10 nm)/B4 PyMPM (50 nm)/LiF (1 nm)/Al (150 nm) and performing device performance test according to the organic electroluminescent device test method.
Specific data of the performance of each organic electroluminescent device prepared above are listed in table 1 below.
Table 1:
/>
the organic electroluminescent device prepared in the above example 1 is shown in fig. 2 and fig. 3, where fig. 2 is an electroluminescent spectrum of the device OLED1, and fig. 3 is an external quantum efficiency-current density curve of the device OLED 1.
As can be seen from the comparison of the performance of the embodiment of the device prepared by the invention, the organic electroluminescent device prepared by the preferred compound of the invention has the advantages of longer luminous wavelength, high luminous efficiency, narrow half-peak width, high spectral color purity and the like. The analysis of specific causes is as follows: the rigid condensed ring structural molecule designed by the invention has a plurality of electron-withdrawing units and a plurality of electron-donating units, so that the charge transfer between a donor unit and an acceptor unit in the molecule can be effectively promoted, and the excited state energy can be effectively stabilized; on the other hand, the molecules have a relatively planar condensed ring large pi conjugated structure, which can realize effective conjugated delocalization of pi electrons on aromatic rings, so that the light emission of the molecules can effectively realize near infrared light emission, and the light emission is obviously red-shifted compared with the material device in the comparative example. It is worth mentioning that pure near infrared luminescence is critical for applications of organic materials and devices in the near infrared field. Because the central skeleton structure of the molecule designed by the invention has a structure adjacent to electron-withdrawing boron atoms and electron-donating nitrogen atoms, the molecular orbit still has the characteristic of multiple resonances, which is favorable for realizing small recombination energy and non-radiative transition rate, and realizing high luminous efficiency and narrow half-peak width. More importantly, the molecules designed by the invention have a rigid structure, on one hand, the vibration and rotation of the molecules can be effectively inhibited, and the recombination energy is reduced, so that the molecules have narrower half-peak width and lower non-radiative transition rate; on the other hand, the front orbits of the rigid condensed ring molecules are distributed on the condensed ring structure, so that the excited state of the rigid condensed ring molecules has high transition dipole and high radiation transition rate, and the high-efficiency luminescence is realized. At the same time, the rigid structure endows the molecules with high stability, so that the material has long service life when in use, and the corresponding device also has long service life. Further, by adopting single bonds and A1, A2 or A3 bridging groups with weak electron donating groups in four X groups on two sides of the molecule, a rigid closed-loop structure can be formed, so that the problem of structural relaxation caused by electron transition is further suppressed, efficient luminescence is facilitated, and meanwhile, the bond energy of the molecule can be further improved due to the formation of the closed-loop structure, so that the stability of the molecule is improved. In terms of electronic structure, the single bond and the A1, A2 or A3 bridging group with weak electron supply have little influence on the electronic structure of the central framework, so that the excellent luminescent property of the central framework is maintained; on the other hand, the introduction of the single bond and the A1, A2 or A3 bridging group with weak electron supply can effectively increase the delocalization degree and the conjugation degree of electrons on the parent nucleus, thereby being beneficial to realizing the further red shift of the luminescence of the material and promoting the radiation transition to realize the high-efficiency luminescence. Furthermore, the four bridging positions on two sides of the molecule can be X groups or X-free groups with different structure types, and the combination optimization design of single bond, A1, A2, A3 or X-free groups is adopted independently for the four bridging positions on two sides of the molecule, so that the regulation and control of the charge transfer intensity in the molecule can be realized, and the effective regulation and control of the photophysical property of the molecule can be further realized. It is worth mentioning that such rigid condensed ring structure molecules possess excellent bipolar transport properties due to the simultaneous electron donating nitrogen atoms and electron withdrawing boron atoms. Meanwhile, the HOMO and LUMO energy levels of the molecules can be regulated and controlled through the combination and optimization of the groups at the bridging positions, so that the energy levels of the molecules are more matched with the energy levels of the transmission layer materials in the device, and the higher efficiency of the device is realized. In addition, the rigid condensed ring structure derivative can further regulate the physical and chemical properties of the molecule through substituent groups on each Ar ring in the mother nucleus. In conclusion, the derivative with the rigid condensed ring structure can be applied to an organic electroluminescent device, so that high-efficiency electroluminescence with high color purity and long service life of the device can be obtained.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (12)

1. A fused ring aromatic compound having a structure represented by the following formula I or II:
in the formula I, ar1 ring, ar2 ring, ar3 ring, ar4 ring, ar5 ring and Ar6 ring each independently represent one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted anthryl;
X 1 、X 2 、X 3 、X 4 each independently selected from a single bond or any of the structures shown below, "×" represents the access bond position of a group:
n1, n2, n3, n4 are each independently 1 or 0;
in the formula II, ar7 ring, ar8 ring, ar9 ring, ar10 ring, ar11 ring, ar12 ring, ar13 ring and Ar14 ring each independently represents one of substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted anthryl;
X 5 、X 6 、X 7 、X 8 each independently selected from a single bond or any of the structures shown below, "×" represents the access bond position of a group:
n5, n6, n7, n8 are each independently 1 or 0;
when substituents on Ar1 ring, ar2 ring, ar3 ring, ar4 ring, ar5 ring, ar6 ring, ar7 ring, ar8 ring, ar9 ring, ar10 ring, ar11 ring, ar12 ring, ar13 ring, ar14 ring represent each independently a substituent of up to the maximum permissible number of substituents, and adjacent two substituents may be linked by a single bond to form a ring, each substituent is independently selected from deuterium, halogen, cyano, C1-C36 chain alkyl, C1-C36 chain alkenyl, C1-C36 chain alkynyl, C3-C36 cycloalkyl, C4-C36 cycloalkenyl, C4-C36 cycloalkynyl, C1-C30 alkoxy, C1-C30 thioalkoxy, carboxy, nitro, silicon-based, amino, C6-C30 arylamino, C3-C30 heteroarylamino, phenyl, C8-C60 fused ring aryl, C6-C60 aryloxy, C4-C60 fused ring heteroaryl, C1-C10 halogen, or a combination of two of C1-C60 fused ring alkoxy groups;
And, the compound represented by formula I or II is not selected from the following compounds:
2. the fused ring aromatic compound according to claim 1, wherein the Ar1 ring, ar2 ring, ar3 ring, ar4 ring, ar5 ring, ar6 ring, ar7 ring, ar8 ring, ar9 ring, ar10 ring, ar11 ring, ar12 ring, ar13 ring, ar14 ring are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl;
when a substituent is present on the above groups, the substituent is independently selected from one of deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 haloaryl, phenyl, C8-C60 fused ring aryl, C6-C60 aryloxy, C4-C60 fused ring heteroaryl.
3. The fused ring aromatic compound according to claim 1, wherein each of the Ar1 ring, ar2 ring, ar3 ring, ar4 ring, ar5 ring, ar6 ring, ar7 ring, ar8 ring, ar9 ring, ar10 ring, ar11 ring, ar12 ring, ar13 ring, ar14 ring is independently selected from a substituted or unsubstituted phenyl group;
when a substituent is present on the above groups, the substituent is independently selected from one of deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 haloaryl, phenyl, C8-C60 fused ring aryl, C6-C60 aryloxy, C4-C60 fused ring heteroaryl.
4. The fused ring aromatic compound according to claim 1, having a structure represented by the following formula I-1 or formula II-1:
in the formula I-1, Z 1 -Z 16 Each independently selected from CR 1 ，R 1 Selected from hydrogen, deuterium, halogen, cyano, C1-C10Chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 haloaryl, phenyl, C8-C60 fused ring aryl, C6-C60 aryloxy, C4-C60 fused ring heteroaryl, when Z 1 -Z 16 Wherein two adjacent rings are present and are located on the same ring are each selected from CR 1 When the two R's are 1 The two can be connected into a ring through a single bond; the X is 1 、X 2 、X 3 、X 4 The definitions of n1, n2, n3, n4 are the same as in formula I;
in the formula I-1, Y 1 -Y 8 Each independently selected from C, CR 2 And Y when n1 is 1 1 And Y 2 All are C, Y when n2 is 1 3 And Y 4 All are C, Y when n3 is 1 5 And Y 6 All are C, Y when n4 is 1 7 And Y 8 All are C, R 2 One selected from deuterium, halogen, cyano, C1-C4 chain alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy;
in formula II-1, Z 21 -Z 42 Each independently selected from CR 3 ，R 3 One selected from hydrogen, deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 haloaryl, phenyl, C8-C60 condensed ring aryl, C6-C60 aryloxy, C4-C60 condensed ring heteroaryl, when Z 21 -Z 42 Wherein two adjacent rings are present and are located on the same ring are each selected from CR 2 When the two R's are 2 The two can be connected into a ring through a single bond; the X is 5 、X 6 、X 7 、X 8 N5, n6, n7, n8 are as defined in formula II;
in formula II-1, Y 21 -Y 28 Each independently selected from C, CR 4 And Y when n5 is 1 21 And Y 22 All are C, Y when n6 is 1 23 And Y 24 All are C, when n7 isY at 1 25 And Y 26 All are C, Y when n8 is 1 27 And Y 28 All are C, R 4 One selected from deuterium, halogen, cyano, C1-C4 chain alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy.
5. The fused ring aromatic compound according to claim 4, wherein the R 1 And R is 3 Each independently selected from one of hydrogen, deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tert-butyl, trifluoromethyl, pentafluoroethyl, phenyl, carbazolyl;
the R is 2 And R is 4 Each independently selected from one of hydrogen, deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tert-butyl, trifluoromethyl, pentafluoroethyl.
6. The condensed ring aromatic compound according to claim 4, which has a structure represented by the following formula I-2 or formula II-2:
in formula I-2, R1-R16 are each independently selected from one of hydrogen, deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloalkyl, C1-C10 alkoxy, C1-C10 haloalkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 haloaryl, phenyl, C8-C60 fused ring aryl, C6-C60 aryloxy, C4-C60 fused ring heteroaryl, and adjacent two of R1-R16 groups attached to the same benzene ring may be joined by a single bond to form a ring; the X is 1 、X 2 、X 3 、X 4 N1, n2, n3, n4 are as defined in formula I, Y 1 -Y 8 Is as defined in formula I-1;
in formula II-2, R21-R42 are each independently selected from hydrogen, deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 haloAlkyl, C1-C10 alkoxy, C1-C10 halogenated alkoxy, C6-C30 aryl amino, C3-C30 heteroaryl amino, C6-C60 halogenated aryl, phenyl, C8-C60 condensed ring aryl, C6-C60 aryloxy, C4-C60 condensed ring heteroaryl, and two adjacent groups of R21-R42 connected on the same benzene ring can be connected into a ring through a single bond; the X is 5 、X 6 、X 7 、X 8 N5, n6, n7, n8 are as defined in formula II, Y 21 -Y 28 Is defined as in formula II-1.
7. The fused ring aromatic compound according to claim 6, wherein R1, R8, R9, R16 are hydrogen or deuterium, and R2 to R7, R10 to R15 are each independently selected from one of deuterium, halogen, cyano, C1 to C10 chain alkyl, C3 to C10 cycloalkyl, C1 to C10 haloalkyl, C1 to C10 alkoxy, C1 to C10 haloalkoxy, C6 to C30 arylamino, C3 to C30 heteroarylamino, C6 to C60 haloaryl, phenyl, C8 to C60 fused ring aryl, C6 to C60 aryloxy, C4 to C60 fused ring heteroaryl;
In the formula II-2, R21, R28, R29, R31, R32, R39, R40 and R42 are hydrogen or deuterium, and R22-R27, R30, R33-R38 and R41 are respectively and independently selected from one of deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 halogenated alkyl, C1-C10 alkoxy, C1-C10 halogenated alkoxy, C6-C30 arylamino, C3-C30 heteroaryl amino, C6-C60 halogenated aryl, phenyl, C8-C60 condensed ring aryl, C6-C60 aryloxy and C4-C60 condensed ring heteroaryl.
8. The fused ring aromatic compound according to claim 6, wherein each of R1 to R16 is independently selected from one of hydrogen, deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tert-butyl, trifluoromethyl, pentafluoroethyl, phenyl, carbazolyl;
in the formula II-2, R21-R42 are each independently selected from one of hydrogen, deuterium, cyano, methyl, ethyl, methoxy, isopropyl, tertiary butyl, trifluoromethyl, pentafluoroethyl, phenyl and carbazolyl.
9. The fused ring aromatic compound according to claim 1, wherein n1, n2, n3, n4 are each 1, and X 1 、X 2 、X 3 、X 4 Are all single bond structures;
alternatively, n1, n2, n3, n4 are all 1, X 1 、X 2 、X 3 、X 4 All have the structure shown in A1;
alternatively, n1, n2, n3, n4 are all 1, X 1 、X 2 、X 3 、X 4 All have the structure shown as A2;
alternatively, n1, n2, n3, n4 are all 1, X 1 、X 2 、X 3 、X 4 All have the structure shown in A3;
or, the structures of n1, n2, n3 and n4 are all 0;
alternatively, n1, n2, n3, n4 are all 1, X 1 And X is 3 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n2, n3, n4 are all 1, X 1 And X is 4 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n2, n3, n4 are all 1, X 1 And X is 3 Is the same and is selected from one of single bond, A1, A2 or A3, and X 2 And X is 4 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n2, n3, n4 are all 1, X 1 And X is 4 Is the same and is selected from one of single bond, A1, A2 or A3, and X 2 And X is 3 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n3 are 1, n2, n4 are 0, and X is 1 And X is 3 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n1, n4 are 1, n2, n3 are 0, and X is 1 And X is 4 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
In the formula II, n5, n6, n7 and n8 are all 1, and X 5 、X 6 、X 7 、X 8 Are all single bond structures;
alternatively, the n5, n6, n7, n8 are all 1, X 5 、X 6 、X 7 、X 8 All have the structure shown in A1;
alternatively, the n5, n6, n7, n8 are all 1, X 5 、X 6 、X 7 、X 8 All have the structure shown as A2;
alternatively, the n5, n6, n7, n8 are all 1, X 5 、X 6 、X 7 、X 8 All have the structure shown in A3;
or, the structures of n5, n6, n7 and n8 are all 0;
alternatively, n5, n6, n7, n8 are all 1, X 5 And X is 7 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n5, n6, n7, n8 are all 1, X 5 And X is 8 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n5, n6, n7, n8 are all 1, X 5 And X is 7 Is the same and is selected from one of single bond, A1, A2 or A3, and X 6 And X is 8 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n5, n6, n7, n8 are all 1, X 5 And X is 8 Is the same and is selected from one of single bond, A1, A2 or A3, and X 6 And X is 7 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
alternatively, n5, n7 are 1, n6, n8 are 0, and X is 5 And X is 7 The compounds are the same and are selected from one of single bond, A1, A2 or A3;
Alternatively, n5, n8 are 1, n6, n7 are 0, and X is 5 And X is 8 And is the same as or simultaneously selected from one of single bond, formula A1, A2 or A3.
10. A fused ring aromatic compound having the structure shown below:
/>
/>
/>
11. use of a polycyclic aromatic compound according to any one of claims 1-10 as a functional material in an organic electronic device selected from the group consisting of: organic electroluminescent devices, optical sensors, solar cells, lighting elements, organic thin film transistors, organic field effect transistors, information labels, electronic artificial skin sheets, sheet scanners or electronic paper.
12. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between the first electrode and the second electrode, characterized in that the organic layer comprises at least one compound according to any one of claims 1 to 10.
CN202011447096.8A 2020-12-09 2020-12-09 Condensed ring aromatic compound and application thereof in electroluminescent device Active CN114621269B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011447096.8A CN114621269B (en) 2020-12-09 2020-12-09 Condensed ring aromatic compound and application thereof in electroluminescent device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011447096.8A CN114621269B (en) 2020-12-09 2020-12-09 Condensed ring aromatic compound and application thereof in electroluminescent device

Publications (2)

Publication Number Publication Date
CN114621269A CN114621269A (en) 2022-06-14
CN114621269B true CN114621269B (en) 2024-04-09

Family

ID=81894664

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011447096.8A Active CN114621269B (en) 2020-12-09 2020-12-09 Condensed ring aromatic compound and application thereof in electroluminescent device

Country Status (1)

Country Link
CN (1) CN114621269B (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109192874A (en) * 2018-08-31 2019-01-11 昆山国显光电有限公司 A kind of organic electroluminescence device and display device
CN109411634A (en) * 2018-08-31 2019-03-01 昆山国显光电有限公司 A kind of organic electroluminescence device and display device
CN110729408A (en) * 2019-10-23 2020-01-24 昆山国显光电有限公司 Organic electroluminescent device and display device
CN110872316A (en) * 2019-11-29 2020-03-10 清华大学 Novel compound, application thereof and organic electroluminescent device using compound
CN111153919A (en) * 2020-01-08 2020-05-15 清华大学 Luminescent material, application thereof and organic electroluminescent device comprising luminescent material
WO2020105990A1 (en) * 2018-11-19 2020-05-28 에스에프씨 주식회사 Novel boron compound and organic light-emitting device comprising same
WO2020106032A1 (en) * 2018-11-20 2020-05-28 에스에프씨 주식회사 Novel boron compound and organic light-emitting device comprising same
CN112174992A (en) * 2020-09-30 2021-01-05 清华大学 Luminescent material, application thereof and organic electroluminescent device comprising luminescent material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109192874A (en) * 2018-08-31 2019-01-11 昆山国显光电有限公司 A kind of organic electroluminescence device and display device
CN109411634A (en) * 2018-08-31 2019-03-01 昆山国显光电有限公司 A kind of organic electroluminescence device and display device
WO2020105990A1 (en) * 2018-11-19 2020-05-28 에스에프씨 주식회사 Novel boron compound and organic light-emitting device comprising same
WO2020106032A1 (en) * 2018-11-20 2020-05-28 에스에프씨 주식회사 Novel boron compound and organic light-emitting device comprising same
CN110729408A (en) * 2019-10-23 2020-01-24 昆山国显光电有限公司 Organic electroluminescent device and display device
CN110872316A (en) * 2019-11-29 2020-03-10 清华大学 Novel compound, application thereof and organic electroluminescent device using compound
CN111153919A (en) * 2020-01-08 2020-05-15 清华大学 Luminescent material, application thereof and organic electroluminescent device comprising luminescent material
CN112174992A (en) * 2020-09-30 2021-01-05 清华大学 Luminescent material, application thereof and organic electroluminescent device comprising luminescent material

Also Published As

Publication number Publication date
CN114621269A (en) 2022-06-14

Similar Documents

Publication Publication Date Title
WO2022257817A1 (en) Organic electroluminescent device and display apparatus
CN112174992B (en) Luminescent material, application thereof and organic electroluminescent device comprising luminescent material
WO2021008374A1 (en) Novel compound and application thereof, and organic electroluminescent device using same
WO2023284103A1 (en) Organic compound and application thereof
CN113717172A (en) Organic compound, application thereof and organic electroluminescent device comprising organic compound
CN113788852A (en) Luminescent material, application thereof and organic electroluminescent device comprising luminescent material
CN112375071B (en) Organic light-emitting compound and preparation method and application thereof
CN115197252A (en) Organic compound and application thereof
CN114685355A (en) Organic compound for organic electroluminescent device, and organic electroluminescent device
CN113921740B (en) Organic electroluminescent device and display device
CN110256439B (en) Organic electroluminescent material and device
Ye et al. AIEE-active blue-emitting molecules derived from methoxyl-decorated triarylcyclopentadienes: Synthesis, crystal structures, photophysical and electroluminescence properties
CN111285877B (en) Organic electroluminescent material and device
CN111303157A (en) Naphthopyrazine derivative, preparation method thereof and electronic device
CN114621269B (en) Condensed ring aromatic compound and application thereof in electroluminescent device
CN115197251A (en) Organic compound and application thereof
CN114621270B (en) Condensed ring aromatic compound and application thereof in electroluminescent device
CN110746425B (en) Organic compound and application thereof
CN114478267A (en) Organic compound for light emitting device and organic electroluminescent device
CN113880869A (en) Compound, application thereof and organic electroluminescent device comprising compound
CN113943287B (en) Polycyclic aromatic compound and application thereof in electroluminescent device
CN113292552B (en) Benzo five-membered ring aza derivative containing benzophenone group and preparation method and application thereof
CN113943290A (en) Polycyclic aromatic compound and application thereof in electroluminescent device
CN114685353A (en) Organic compound for organic light emitting device, organic electroluminescent device
CN116478191A (en) Luminescent material, application thereof and organic electroluminescent device comprising luminescent material

Legal Events

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