COMPOUND AND USE THEREOF IN ORGANIC OPTOELECTRONIC DEVICE
20250098525 · 2025-03-20
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Inventors
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C07D409/12
CHEMISTRY; METALLURGY
H10K85/6574
ELECTRICITY
C07D409/04
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H10K85/6572
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C07D405/10
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C07D211/26
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H10K85/636
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C07D417/10
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Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
H10K85/6576
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C07D407/12
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C07D209/88
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C07C211/61
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C07D235/06
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C07D405/12
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C07D265/38
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C07D403/12
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H10K85/626
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C07D401/12
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C07D405/04
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C07D241/42
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C07D209/90
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C07D403/04
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H10K85/633
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C07D413/12
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H10K85/615
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International classification
C07C211/61
CHEMISTRY; METALLURGY
C07D209/88
CHEMISTRY; METALLURGY
C07D409/12
CHEMISTRY; METALLURGY
C07D209/90
CHEMISTRY; METALLURGY
C07D235/06
CHEMISTRY; METALLURGY
C07D413/12
CHEMISTRY; METALLURGY
C07D401/12
CHEMISTRY; METALLURGY
C07D405/12
CHEMISTRY; METALLURGY
C07D211/26
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C07D241/42
CHEMISTRY; METALLURGY
C07D265/38
CHEMISTRY; METALLURGY
C07D409/04
CHEMISTRY; METALLURGY
C07D405/04
CHEMISTRY; METALLURGY
C07D403/04
CHEMISTRY; METALLURGY
C07D405/10
CHEMISTRY; METALLURGY
C07D403/12
CHEMISTRY; METALLURGY
C07D407/12
CHEMISTRY; METALLURGY
C07D417/10
CHEMISTRY; METALLURGY
Abstract
Embodiments are related to the field of organic electroluminescent materials, and in particular to a compound and a use thereof in an organic optoelectronic device. The chemical structure of the compound is as shown in formula (I). The compound is applied to an organic device, which enables the device to have high hole mobility, and to effectively prevent electrons and excitons from entering a hole transport layer, thereby improving the efficiency of the device. In addition, the molecule has high stability, which further improves the light-emitting efficiency and the service life of the device.
##STR00001##
Claims
1. A compound, wherein a chemical structure of the compound is shown in formula (II): ##STR00350## where R.sub.1-R.sub.2 are each independently selected from hydrogen or deuterium; R.sub.9 and R.sub.10 are independently selected from substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C6-C30 aryl groups; or, R.sub.9 and R.sub.10 are bonded to adjacent groups to form a ring; group A is selected from ##STR00351## R.sub.16-R.sub.23 are each independently selected one or more from hydrogen, deuterium, substituted or unsubstituted C1-C60 alkyl groups, substituted or unsubstituted C1-C60 cycloalkyl groups, substituted or unsubstituted C1-C60 heteroalkyl groups, substituted or unsubstituted C1-C60 heterocycloalkyl groups, substituted or unsubstituted C1-C60 aryl groups, or substituted or unsubstituted C1-C60 heteroaryl groups; is a connection site of an atom, a single link or multiple links are included at the connection site; the connection site is in a ring of group A, or represents any position of the shown groups, or represents bonding with adjacent atoms to form a ring; L.sub.2-L.sub.3 are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted anthrylene group; and Ar.sub.1 and Ar.sub.2 are the same or different, and are each independently selected from substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups.
2. The compound of claim 1, wherein it is selected from following chemical structural formulas indicated by formula (III) to (VI): ##STR00352## where R.sub.1, R.sub.2, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined as in claim 1.
3. The compound of claim 2, wherein ring A is selected from following structures: ##STR00353##
4. The compound of claim 1, wherein the chemical structure of the compound is as shown in formula (VII): ##STR00354## where R.sub.1 and R.sub.2 are each independently selected from hydrogen or deuterium; R.sub.9, R.sub.10, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in claim 1.
5. The compound of claim 4, wherein the chemical structure of the compound is as shown in formulas (VIII) to (XI): ##STR00355## where R.sub.1, R.sub.2, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in claim 4.
6. The compound of claim 1, wherein Ar.sub.1 and Ar.sub.2 are each independently selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, ##STR00356##
7. The compound of claim 1, wherein the compound is any one selected from following chemical structures: ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363## ##STR00364## ##STR00365## ##STR00366##
8. The compound of claim 3, wherein the chemical structure of the compound is selected from following structures: ##STR00367## where Ar.sub.1 and Ar.sub.2 are each independently selected from phenyl, diphenyl, terphenyl, naphthyl, phenanthryl, dimethylfluorene, diphenylfluorene, spirofluorene, dibenzothienyl, dibenzofuranyl, carbazolyl, or a combination of any two of these groups; when Ar.sub.1 and Ar.sub.2 are selected from dimethylfluorene, diphenylfluorene, and spirofluorene, their adjacent N position is not connected with other groups; Ar.sub.1 and Ar.sub.2 are not selected as a combination of diphenyl and carbazolyl.
9. A compound, wherein a chemical structure of the compound is shown in formula (I): ##STR00368## where group A is one or more selected from of the following groups: ##STR00369## Z.sub.1-Z.sub.75, Z.sub.76Z.sub.121 are each independently selected from CR.sub.3R.sub.4, NR.sub.5, SiR.sub.6R.sub.7, BRs, O or S; *1, *2 are connection sites of group A; *1 or *2 is capable of being connected to any position on group A; X.sub.1, X.sub.2 are each independently selected from a single bond, CR.sub.9R.sub.10, NR.sub.11, SiR.sub.12R.sub.13, O or S; or R.sub.9, R.sub.10 are bonded to form a ring; R.sub.1-R.sub.3 are the same or different, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C30 heteroalkyl groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups; L.sub.1-L.sub.3 are the same or different, and are each independently selected from a single bond, substituted or unsubstituted C6-C30 arylene groups, or substituted or unsubstituted C3-C30 heteroarylene groups; Ar.sub.1 and Ar.sub.2 are the same or different, and are each independently selected from substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups.
10. The compound of claim 9, wherein group A is any one selected from following groups: ##STR00370## ##STR00371## ##STR00372## where R.sub.16-R.sub.23 are each independently selected one or more from hydrogen, deuterium, substituted or unsubstituted C1-C60 alkyl groups, substituted or unsubstituted C1-C60 cycloalkyl groups, substituted or unsubstituted C1-C60 heteroalkyl groups, substituted or unsubstituted C1-C60 heterocycloalkyl groups, substituted or unsubstituted C1-C60 aryl groups, or substituted or unsubstituted C1-C60 heteroaryl groups; is a connection site of an atom.
11. The compound of claim 9, wherein group A is any one selected from following groups: ##STR00373## ##STR00374## ##STR00375##
12. The compound of claim 9, wherein X.sub.1 and X.sub.2 are each independently selected from a single bond, O, S, ##STR00376##
13. The compound of claim 9, wherein R.sub.1 and R.sub.2 are each independently selected from hydrogen or deuterium; and/or, R.sub.3-R.sub.13 are the same or different, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C12 alkoxy groups, substituted or unsubstituted C1-C12 alkylthio groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups; wherein L.sub.1-L.sub.3 are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrenyl group, ##STR00377## ##STR00378## and Ar.sub.3 is selected from C6-C20 aryl groups or C2-C15 heteroaryl groups; wherein Ar.sub.1 and Ar.sub.2 are each independently selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, ##STR00379##
14. The compound of claim 9, wherein the chemical structure of the compound is as shown in formula (II): ##STR00380## where R.sub.1 and R.sub.2 are each independently selected from hydrogen or deuterium; R.sub.9 and R.sub.10 are independently selected from substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C12 alkoxy groups, substituted or unsubstituted C1-C12 alkylthio groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups; or, R.sub.9 and R.sub.10 are bonded to adjacent groups to form a ring; and A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in claim 9.
15. The compound of claim 14, wherein it is selected from following chemical structural formulas indicated by formula (III) to (VI): ##STR00381## where R.sub.1, R.sub.2, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined as in claim 14.
16. The compound of claim 15, wherein ring A is selected from following structures: ##STR00382##
17. The compound of claim 9, wherein the chemical structure of the compound is as shown in formula (VII): ##STR00383## where R.sub.1 and R.sub.2 are each independently selected from hydrogen or deuterium; R.sub.9 and R.sub.10 are independently selected from substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C12 alkoxy groups, substituted or unsubstituted C1-C12 alkylthio groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups; or, R.sub.9 and R.sub.10 are bonded to adjacent groups to form a ring; and A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in claim 9.
18. The compound of claim 17, wherein the chemical structure of the compound is as shown in formula (VIII) to (XI): ##STR00384## R.sub.1, R.sub.2, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in claim 17.
19. The compound of claim 9, wherein the compound is any one selected from following chemical structures: ##STR00385## ##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400## ##STR00401## ##STR00402## ##STR00403## ##STR00404## ##STR00405## ##STR00406## ##STR00407## ##STR00408## ##STR00409## ##STR00410## ##STR00411## ##STR00412## ##STR00413## ##STR00414## ##STR00415## ##STR00416## ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## ##STR00422## ##STR00423## ##STR00424## ##STR00425## ##STR00426## ##STR00427## ##STR00428## ##STR00429## ##STR00430## ##STR00431## ##STR00432## ##STR00433## ##STR00434## ##STR00435## ##STR00436## ##STR00437## ##STR00438## ##STR00439## ##STR00440## ##STR00441## ##STR00442## ##STR00443## ##STR00444## ##STR00445## ##STR00446## ##STR00447## ##STR00448## ##STR00449## ##STR00450## ##STR00451## ##STR00452## ##STR00453## ##STR00454## ##STR00455## ##STR00456## ##STR00457## ##STR00458## ##STR00459## ##STR00460## ##STR00461## ##STR00462## ##STR00463## ##STR00464## ##STR00465## ##STR00466## ##STR00467## ##STR00468## ##STR00469## ##STR00470## ##STR00471## ##STR00472## ##STR00473## ##STR00474## ##STR00475## ##STR00476## ##STR00477## ##STR00478## ##STR00479## ##STR00480## ##STR00481## ##STR00482## ##STR00483## ##STR00484## ##STR00485## ##STR00486## ##STR00487## ##STR00488## ##STR00489## ##STR00490## ##STR00491## ##STR00492## ##STR00493## ##STR00494## ##STR00495## ##STR00496## ##STR00497## ##STR00498## ##STR00499## ##STR00500## ##STR00501## ##STR00502## ##STR00503## ##STR00504## ##STR00505## ##STR00506## ##STR00507## ##STR00508## ##STR00509## ##STR00510## ##STR00511## ##STR00512## ##STR00513## ##STR00514## ##STR00515## ##STR00516## ##STR00517## ##STR00518## ##STR00519## ##STR00520## ##STR00521## ##STR00522## ##STR00523## ##STR00524## ##STR00525## ##STR00526## ##STR00527## ##STR00528## ##STR00529## ##STR00530## ##STR00531## ##STR00532## ##STR00533## ##STR00534## ##STR00535## ##STR00536## ##STR00537## ##STR00538## ##STR00539## ##STR00540## ##STR00541## ##STR00542## ##STR00543## ##STR00544## ##STR00545## ##STR00546## ##STR00547## ##STR00548## ##STR00549## ##STR00550## ##STR00551## ##STR00552## ##STR00553## ##STR00554## ##STR00555## ##STR00556## ##STR00557## ##STR00558## ##STR00559## ##STR00560## ##STR00561## ##STR00562## ##STR00563## ##STR00564## ##STR00565## ##STR00566## ##STR00567## ##STR00568## ##STR00569## ##STR00570## ##STR00571## ##STR00572##
20. An organic optoelectronic device, comprising a first electrode, a second electrode and an organic layer, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer or an electron transport layer, and the organic layer comprising a compound having a chemical structure shown in formula (I): ##STR00573## where group A is one or more selected from of the following groups: ##STR00574## Z.sub.1-Z.sub.75, Z.sub.76-Z.sub.121 are each independently selected from CR.sub.3R.sub.4, NR, SiR.sub.6R.sub.7, BRs, O or S; *1, *2 are connection sites of group A; *1 or *2 is capable of being connected to any position on group A; X.sub.1, X.sub.2 are each independently selected from a single bond, CR.sub.9R.sub.10, NR.sub.11, SiR.sub.12R.sub.13, 0 or S; or R.sub.9, R.sub.10 are bonded to form a ring; R.sub.1-R.sub.13 are the same or different, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C30 heteroalkyl groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups; L.sub.1-L.sub.3 are the same or different, and are each independently selected from a single bond, substituted or unsubstituted C6-C30 arylene groups, or substituted or unsubstituted C3-C30 heteroarylene groups; A.sub.1 and Ar.sub.2 are the same or different, and are each independently selected from substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups.
Description
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0024] Hereinafter, the embodiments of the compound and use thereof in organic optoelectronic devices are described in detail. Those skilled in the art can easily understand other advantages and effects of the present disclosure from the contents disclosed in this specification. The present disclosure may also be implemented or applied through other different specific implementations, and the details in this specification may also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present disclosure.
[0025] Before further describing the specific embodiments of the present disclosure, it should be understood that the scope of protection of the present disclosure is not limited to the specific embodiments described below. It should also be understood that the terms used in the examples of the present disclosure are for describing the specific embodiments rather than limiting the scope of protection of the present disclosure. In the present specification and claims, unless otherwise expressly stated herein, the singular forms a, an and this include plural forms.
[0026] When numerical ranges are given in the embodiments, it should be understood that the two endpoints of each numerical range and any numerical value between the two endpoints can be used unless otherwise specified in the present disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art. In addition to the specific methods, equipment, and materials used in the embodiments, based on the understanding of the prior art by those skilled in the art and the description of the present disclosure, any methods, equipment, and materials of the prior art that are similar or equivalent to the methods, equipment, and materials described in the embodiments of the present disclosure may also be used to implement the present disclosure.
[0027] After extensive research, the inventors of the present disclosure provide a compound based on a series of benzoalkyl. The inventors of the present disclosure found that, by introducing benzoalkane derivatives into a triarylamine system, a series of hole transport materials with excellent performance were obtained. The introduction of the benzoalkane derivatives near the nitrogen atom was originally intended to improve the mobility of the material by utilizing the electron-donating properties of the aliphatic ring. Generally, the thermal stability and service life of the material would decrease after the introduction of the aliphatic ring. However, what is unexpected is that, the lifetime of this material is greatly improved. There are two possible reasons: 1) the introduction of the benzoalkyl group leads to an increase in the steric hindrance between molecular groups, thereby increasing the triplet energy level of the molecules, increasing the triplet stability of the molecules and further increasing the lifetime of the material; and 2) there is a weak conjugation between the benzoalkyl group and the nitrogen atom, which can stabilize the molecule and thus increase the lifetime of the material. Therefore, this type of compound can not also improve the mobility, but also provide a long service life for the OLED device. On this basis, the present disclosure is proposed.
[0028] Examples of substituents in the present disclosure are described below, but the substituents are not limited thereto.
[0029] [Substituted or unsubstituted] means being substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amino group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, a boron group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, an alkylamine group, an aralkylamine group, a heteroarylamine group, an arylamine group, an arylphosphino group and a heteroaryl group, an acenaphthenyl group, a compound group; or being unsubstituted; alternatively, being substituted with a substituent connecting two or more of the substituents exemplified above, or being unsubstituted. For example, a substituent connecting two or more substituents may include a biphenyl group, that is, the biphenyl group may be an aryl group, or a substituent connecting two phenyl groups.
[0030] The [alkyl] group may be straight or branched, and the number of carbon atoms therein is not particularly limited. In some embodiments, the alkyl includes, but is not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, and 5-methylhexyl.
[0031] The above description of alkyl also applies to alkyl in the aralkyl group, aralkylamine group, alkylaryl group and alkylamine group.
[0032] The [heteroalkyl group] may be a straight-chain or branched-chain alkyl group containing a heteroatom, and the number of carbon atoms therein is not particularly limited. In some embodiments, the heteroalkyl includes, but is not limited to, alkoxy, alkylthio, alkylsulfonyl, and the like. The alkoxy includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexyloxy, 3,3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, and the like. The alkylthio for example includes, but is not limited to, methylthio, ethylthio, n-propylthio, isopropylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, sec-butylthio, n-pentylthio, neopentylthio, isopentylthio, n-hexylthio, 3,3-dimethylbutylthio, 2-ethylbutylthio, n-octylthio, n-nonylthio, n-decylthio, benzylthio, and the like.
[0033] The [cycloalkyl group] may be cyclic, and the number of carbon atoms therein is not particularly limited. In some embodiments, the cycloalkyl includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like.
[0034] The [heterocycloalkyl group] may be a cycloalkyl group containing a heteroatom, and the number of carbon atoms therein is not particularly limited. In some embodiments, the heterocycloalkyl includes, but is not limited to,
##STR00004##
and the like.
[0035] For [aryl group], there are no particular limitations on the aryl group, and the aryl group may be a monocyclic aryl group or a polycyclic aryl group. In some embodiments, the monocyclic aryl group includes, but is not limited to, phenyl, biphenyl, terphenyl, quaterphenyl, pentphenyl, and the like. The polycyclic aromatic group includes, but is not limited to, naphthyl, anthracenyl, phenanthrenyl, pyrenyl, perylenyl, fluorenyl, and the like. The fluorenyl group may be substituted, for example, 9,9-dimethylfluorenyl, 9,9-dibenzofluorenyl, and the like. In addition, two of the substituents may be combined with each other to form a spiro ring structure, such as 9,9-spirobifluorenyl and the like.
[0036] The above description of the aryl group can be applied to the arylene group, except that the arylene group is divalent.
[0037] The above description of the aryl group may be applied to aryl in the aryloxy group, arylthio group, arylsulfonyl group, arylphosphino group, arylalkyl group, arylalkylamino group, arylalkenyl group, alkylaryl group, arylamine group and arylheteroarylamine group.
[0038] The [heteroaryl group] contains one or more of N, O, P, S, Si and Se as heteroatoms. The heteroaryl includes, but is not limited to, pyridinyl, pyrrolyl, pyrimidinyl, pyridazinyl, furanyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, diazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, azinyl, thiazinyl, dioxinyl, triazinyl, tetrazinyl, quinolyl, isoquinolyl, quinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, phthalazine, triazatruxene, indolyl, indolinyl, indolizinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolecarbazolyl, indenocarbazolyl, phenazinyl, imidazopyridinyl, phenazine, phenanthridinyl, phenanthroline, phenothiazinyl, imidazopyridinyl, imidazophenanthridinyl, benzimidazoquinazolinyl, benzimidazophenanthridinyl, spiro[fluorene-9,9-xanthene], benzophenaphthyl, dinaphthofuranyl, naphthiobenzofuranyl, dinaphthothiophene, naphthiobenzothiophene, triphenylphosphine oxide, triphenylborane, etc.
[0039] The above description of the heteroaryl group may be applied to the heteroaryl in the heteroarylamine group and the arylheteroarylamine group.
[0040] The above description of the heteroaryl group may be applied to heteroarylene group, except that the heteroarylene group is divalent.
[0041] In one aspect, the embodiments of the present disclosure provides a compound, and the chemical structure of the compound is shown in formula (I):
##STR00005## [0042] where group A is one or more selected from the following groups:
##STR00006##
[0043] Z.sub.1-Z.sub.75, Z.sub.76-Z.sub.121 are each independently selected from CR.sub.3R.sub.4, NR.sub.5, SiR.sub.6R.sub.7, BR.sub.8, O or S. *1 and *2 are connection sites of group A, and *1 or *2 is capable of being connected to any position on group A.
[0044] X.sub.1, X.sub.2 are each independently selected from a single bond, CR.sub.9R.sub.10, NR.sub.11, SiR.sub.12R.sub.13, O or S, or R.sub.9, R.sub.10 are bonded to form a ring. A single bond is a type of direct bond. For example, X.sub.1 is a single bond, representing a direct connection to the carbons on two benzene rings connected to X.sub.1. With regard to the ring bonded by R.sub.9 and R.sub.10, it means forming an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, an aliphatic heterocyclic ring, an aromatic heterocyclic ring, or a condensed ring thereof. For example, R.sub.9 and R.sub.10 are bonded to form
##STR00007##
which is combined into formula (I) to form
##STR00008##
[0045] R.sub.1-R.sub.13 are the same or different, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C30 heteroalkyl groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups.
[0046] Among them, R.sub.1 and R.sub.2 not only represent a single substituent group, but also represent multiple identical or different substituent groups. For example, it may be selected from the following structures:
##STR00009##
[0047] L.sub.1-L.sub.3 are the same or different, and each are independently selected from a single bond, substituted or unsubstituted C6-C30 arylene groups, or substituted or unsubstituted C3-C30 heteroarylene groups.
[0048] Ar.sub.1 and Ar.sub.2 are the same or different, and are each independently selected from substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups.
[0049] When Z (Z.sub.1-Z.sub.75, Z.sub.76-Z.sub.121) mentioned above is selected from CR.sub.3R.sub.4, NR.sub.5 or SiR.sub.6R.sub.7, and when X (X.sub.1, X.sub.2) is selected from CR.sub.9R.sub.10, NR.sub.11, or SiR.sub.12R.sub.13, since the fatty alkyl group, the nitrogen atom and the silane group have an electron donating effect, the A ring has an electron donating effect, which can fully stabilize the nitrogen atom of the triarylamine, and make it more stable, thereby improving the lifetime of the material. When Z (Z.sub.1-Z.sub.75, Z.sub.76-Z.sub.121) is selected from BRs, O or S, and when X (X.sub.1, X.sub.2) is selected from O or S, due to the electron-withdrawing properties of BRs, O or S, electrons would shift toward them, thus affecting the lifetime of the material. But surprisingly, in the case where Z (Z.sub.1-Z.sub.75, Z.sub.76-Z.sub.121) is selected from BRs, O or S, when the material is applied to red light devices, there is basically no effect on the lifetime; however, when the material is applied to green light devices, their lifetime is lower than that when Z is selected from groups having the electron-donating effect. The possible reason is that, in the green light devices, the energy of excitons is high and thus there is high stability requirements on the molecules; as thus, there is no difference in lifetime when being used in the red light devices, but has differences in efficiency and lifetime when being used in the green light devices.
[0050] In some embodiments, in formula (I), the number of carbon atoms in the aforementioned alkyl group may also be 1 to 10, 1 to 20, or 20 to 30, etc. The number of carbon atoms in the aforementioned cycloalkyl group may be 3 to 10, 3 to 20, or 3 to 30. The number of carbon atoms in the aforementioned heteroalkyl group may also be 3 to 10, 1 to 20, or 20 to 30. The number of carbon atoms in the aforementioned heterocycloalkyl group may also be 3 to 10, 3 to 20, or 20 to 30. The number of carbon atoms in the aforementioned aryl group may be 6 to 10, 6 to 20, or 20 to 30. The number of carbon atoms in the aforementioned heteroaryl group may also be 6 to 10, 6 to 20, or 20 to 30.
[0051] The above description of the number of carbon atoms in the aryl group and the heteroaryl group is applicable to the arylene group and the heteroarylene group mentioned in the present disclosure.
[0052] In the compound provided by the present disclosure, group A is any one selected from following groups:
##STR00010## ##STR00011## ##STR00012## ##STR00013## [0053] where R.sub.16-R.sub.23 are each independently selected one or more from hydrogen, deuterium, substituted or unsubstituted C1-C60 alkyl groups, substituted or unsubstituted C1-C60 cycloalkyl groups, substituted or unsubstituted C1-C60 heteroalkyl groups, substituted or unsubstituted C1-C60 heterocycloalkyl groups, substituted or unsubstituted C1-C60 aryl groups or substituted or unsubstituted C1-C60 heteroaryl groups.
is the connection site of the atom, which is not limited to a single link, but may also represent multiple links. The connection site is not limited to the ring of the aforementioned group A, but also represents any position of the groups shown. It may also represent bonding with adjacent atoms to form a ring.
[0054] In the compounds provided by the present disclosure, in some embodiments, group A is any one selected from the following groups:
##STR00014##
[0055] Preferably, it is
##STR00015##
[0056] Further, group A is one or more selected from the following groups:
##STR00016## ##STR00017## ##STR00018## ##STR00019##
[0057] In the compounds provided by the present disclosure, X.sub.1 and X.sub.2 are the same or different, and are each independently selected from a single bond, O, S,
##STR00020##
[0058] The above ----- represents a connecting bond, connecting to the adjacent group. For example, in X.sub.1, ------ represents connection to a benzene ring. For example,
##STR00021##
connects to an adjacent benzene ring to form
##STR00022##
For another example, in X.sub.2, ------ represents connection to a benzene ring.
##STR00023##
connects to the adjacent benzene ring to form
##STR00024##
[0059] Considering the simplicity and cost of synthesis, R.sub.1 and R.sub.2 are selected from hydrogen.
[0060] Generally, the lifetime of the material is improved by replacing hydrogen atoms with deuterium atoms, and therefore R.sub.1 and R.sub.2 are preferably selected from deuterium.
[0061] In the compounds provided by the present disclosure, R.sub.3-R.sub.13 are the same or different, and are each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C12 alkoxy groups, substituted or unsubstituted C1-C12 alkylthio groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups.
[0062] In the compounds provided by the present disclosure, the L.sub.1-L.sub.3 are each independently selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrenyl group,
##STR00025## ##STR00026##
and the like. Ar.sub.3 is selected from C6-C20 aryl groups or C2-C15 heteroaryl groups. Ar.sub.3 is preferably phenyl, naphthyl, etc.
[0063] Preferably, L.sub.1-L.sub.3 are each independently selected from phenylene, naphthylene, biphenylene,
##STR00027##
[0064] The above ----- represents a connecting bond, connecting to the adjacent group. For example, in L.sub.2, ----- represents connection with Ar.sub.1 or N. For another example, in L.sub.3, ----- represents connection with Ar.sub.2 or N.
[0065] In the compounds provided by the present disclosure, Ar.sub.1 and Ar.sub.2 are each independently selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group,
##STR00028##
[0066] Considering the simplicity and cost of molecular synthesis, one of X.sub.1 and X.sub.2 is a single bond and the other is CR.sub.9R.sub.10. This can be inferred unambiguously from the compound of formula (I). That is, X.sub.1 is selected from a single bond, X.sub.2 is selected from CR.sub.9R.sub.10, and the following general compound is obtained when other conditions remain unchanged.
##STR00029##
[0067] R.sub.1, R.sub.2, A, L.sub.1, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (I).
[0068] R.sub.9 and R.sub.10 are independently selected from substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C12 alkoxy groups, substituted or unsubstituted C1-C12 alkylthio groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups; or are bonded to adjacent groups to form a ring. From the perspective of simplicity and cost of molecular synthesis, when L.sub.1 is selected from a single bond, one of X.sub.1 and X.sub.2 is a single bond and the other is CR.sub.9R.sub.10. This can be inferred unambiguously from the compound of formula (I). That is, when X.sub.1 is selected from a single bond, X.sub.2 is selected from CR.sub.9R.sub.10, and other conditions remain unchanged, the compound represented by formula (II) is obtained.
##STR00030##
[0069] In which, R.sub.1 and R.sub.2 are each independently selected from hydrogen and deuterium.
[0070] R.sub.9 and R.sub.10 are independently selected from substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C12 alkoxy groups, substituted or unsubstituted C1-C12 alkylthio groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups; or are bonded to adjacent groups to form a ring. A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (I).
[0071] Preferably, X.sub.1 and X.sub.2 described in the specification are each independently selected from a single bond,
##STR00031##
and the like. The chemical formula (II) may be represented by the following structural formula:
##STR00032## [0072] where R.sub.1, R.sub.2, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (II).
[0073] Preferably, ring A is selected from the following structures:
##STR00033##
[0074] Preferably, the compound has the structural formula
##STR00034## [0075] where R.sub.1, R.sub.2, R.sub.9, R.sub.10, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (II).
[0076] Further preferably, the structural formula of the compound is:
##STR00035## [0077] where R.sub.1, R.sub.2, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (II).
[0078] From the perspective of simplicity and cost of molecular synthesis, when L.sub.1 is selected from phenyl, one of X.sub.1 and X.sub.2 is a single bond and the other is CR.sub.9R.sub.10. This can be inferred unambiguously from the compound of formula (I). That is, when X.sub.1 is selected from a single bond, X.sub.2 is selected from CR.sub.9R.sub.10, L.sub.1 is selected from phenyl, and other factors remain unchanged, the compound represented by formula (VII) is obtained.
##STR00036## [0079] where R.sub.1 and R.sub.2 are each independently selected from hydrogen or deuterium.
[0080] In which, R.sub.9 and R.sub.10 are independently selected from substituted or unsubstituted straight or branched C1-C30 alkyl groups, substituted or unsubstituted C1-C12 alkoxy groups, substituted or unsubstituted C1-C12 alkylthio groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C3-C30 heterocycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, or substituted or unsubstituted C6-C30 heteroaryl groups; or are bonded to adjacent groups to form a ring. A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (I).
[0081] Preferably, X.sub.1 and X.sub.2 described in the specification are each independently selected from a single bond,
##STR00037##
and the like. The chemical formula (VII) may be represented by the following structural formula:
##STR00038## [0082] where R.sub.1, R.sub.2, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (VII).
[0083] From the perspective of the cost of synthesis and the availability of raw materials, preferably, the A ring is selected from the following structures:
##STR00039##
[0084] Preferably, the compound has the structural formula
##STR00040## [0085] where R.sub.1, R.sub.2, R.sub.9, R.sub.10, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (VII).
[0086] Further preferably, the structural formula of the compound is:
##STR00041## [0087] where R.sub.1, R.sub.2, A, L.sub.2, L.sub.3, Ar.sub.1, and Ar.sub.2 are as defined in the compound of formula (VII).
[0088] In some embodiments, the chemical structure of the compound is selected from following structures:
##STR00042## [0089] where Ar.sub.1 and Ar.sub.2 are each independently selected from phenyl, diphenyl, terphenyl, naphthyl, phenanthryl, dimethylfluorene, diphenylfluorene, spirofluorene, dibenzothienyl, dibenzofuranyl, carbazolyl, or a combination of any two of these groups. When Ar.sub.1 and Ar.sub.2 are selected from dimethylfluorene, diphenylfluorene, and spirofluorene, their adjacent N position is not connected with other groups. Ar.sub.1 and Ar.sub.2 are not selected as a combination of diphenyl and carbazolyl.
[0090] In the compound provided by the present disclosure, the compound is any one selected from the following chemical structures:
##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069## ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102## ##STR00103## ##STR00104## ##STR00105## ##STR00106## ##STR00107## ##STR00108## ##STR00109## ##STR00110## ##STR00111## ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120## ##STR00121## ##STR00122## ##STR00123## ##STR00124## ##STR00125## ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135##
##STR00136## ##STR00137## ##STR00138## ##STR00139## ##STR00140## ##STR00141## ##STR00142## ##STR00143## ##STR00144## ##STR00145## ##STR00146## ##STR00147## ##STR00148## ##STR00149## ##STR00150## ##STR00151## ##STR00152## ##STR00153## ##STR00154## ##STR00155## ##STR00156## ##STR00157## ##STR00158## ##STR00159## ##STR00160## ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178## ##STR00179## ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206##
[0091] Specifically, the above structure may be unsubstituted or substituted with one or more substituents selected from the following. For example, the substituent may be deuterium, a halogen group, a nitrile group, a nitro group, a hydroxyl group, a carbonyl group, an ester group, an imide group, an amine group, a phosphine oxide group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, a silyl group, a boron group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an aralkyl group, an aralkenyl group, an alkylaryl group, an alkylamine group, an aralkylamine group, a heteroarylamine group, an arylamine group, an arylheteroarylamine group, an arylphosphino group, a heteroaryl group, and the like.
[0092] The compounds of the present disclosure have different material lifetime depending on the different molecular structures and application scenarios. According to the specific conditions of group A and group B (as long as there is one non-carbon atom in group B, it is a heterocyclic structure), the enumerated structures may include the following categories:
##STR00207##
[0093] When X.sub.1 in group B is arbitrarily selected from carbon atoms CR.sub.9R.sub.10, and X.sub.2 does not contain heteroatoms, that is, a single bond or CR.sub.9R.sub.10, since neither the single bond nor CR.sub.9R.sub.10 has strong electron absorption or electron-dominating properties, the effect on the molecular properties is limited. When X.sub.2 is arbitrarily selected from carbon atoms CR.sub.9R.sub.10, and X.sub.1 does not contain heteroatoms, that is, a single bond or CR.sub.9R.sub.10, since neither the single bond nor CR.sub.9R.sub.10 has strong electron absorption or electron-dominating properties, the effect on the molecular properties is limited. These two situations may be classified into a same category. Among them, R.sub.9 R.sub.10, and R.sub.9R.sub.10 are defined in the same way. X.sub.1, X.sub.2 in group B are each independently selected from a single bond, CR.sub.9R.sub.10, NR.sub.11, SR.sub.12R.sub.13, or S. As long as there is a heteroatom in group B (any one of NR.sub.11, SiR.sub.12R.sub.13, O or S), it is classified as a heterocyclic structure, and its performance is greatly affected by the heteroatom and may be classified into one category. For example, when X.sub.1 is selected from any heteroatom NR.sub.11, SiR.sub.12R.sub.13, O or S, regardless of whether X.sub.2 is a single bond, CR.sub.9R.sub.10 or X.sub.2 is the heteroatom NR.sub.11, SiR.sub.12R.sub.13, O or S, the performance is affected by the heteroatom of X.sub.1. Similarly, when X.sub.2 is selected from any heteroatom NR.sub.11, SiR.sub.12R.sub.13, O or S, regardless of whether X.sub.1 is a single bond, CR.sub.9R.sub.10, or it is the heteroatom NR.sub.11, SiR.sub.12R.sub.13, O or S, the performance is affected by the heteroatom X.sub.2. These two situations may be classified into one category. Since the heteroatom NR.sub.11, SiR.sub.12R.sub.13, O or S have a large electronegativity difference, the effect of such electronegativity on the molecules is classified with decreasing in the electronegativity of elements, which varies at a large extent, so the impact on the device performance will vary. According to O, N, the situations are as follows:
TABLE-US-00001 B A X.sub.1(X.sub.2) X.sub.2(X.sub.1) Type Enumerated combination CR.sub.3R.sub.4 CR.sub.9R.sub.10 Single bond or 1 1, 4, 5, 7, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 23, carbon atom 24, 25, 26, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, group 41, 42, 45, 46, 47, 48, 49, 51, 52, 53, 54, 128, 129, 130, 131, 132, 133, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 147, 171, 172, 274, 275, 276, 277, 278, 280, 281, 282, 283, 284, 285, 287, 288, 289, 290, 291, 292, 294, 295, 296, 297, 298, 299, 300, 301, 302, 303, 304, 305, 306, 351, 451, 452, 453, 454, 456, 457, 458, 459, 460, 461, 462, 463, 464, 465, 466, 467, 468, 469, 470, 471, 472, 473, 474, 475, 476, 477, 478, 480, 485, 494, 503, 504, 505, 506, 507, 508, 509, 510, 511, 512, 513, 514, 515, 516, 517, 518, 519, 520, 521, 522, 523, 524, 525, 526, 527, 528 NR.sub.11 N or S or C or 2 3, 43, 127, 279 single bond O O or N or S or C 3 2, 8, 11, 22, 28, 50, 134, 273, 286, 478, 481, 493 or single bond S S or C or single 4 6, 44, 293 bond NR.sub.5 CR.sub.9R.sub.10 Single bond or 5 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, carbon atom 157, 158, 159, 162, 170, 164, 165, 166, 167, 168, 169, group 171, 172, 173, 174, 176, 177, 179, 180, 181, 182, 184, 186, 187, 188, 189, 190, 191, 192, 193, 195, 196, 198, 199, 200, 201, 202, 203, 205, 206, 207, 208, 209, 210, 211, 212, 214, 215, 216, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 257, 258, 259, 260, 261, 262, 264, 265, 266, 267, 270, 308, 309, 310, 311, 312, 313, 314, 315, 316, 317, 318, 319, 320, 321, 322, 323, 324, 325, 326, 327, 328, 329, 330, 331, 332, 333, 334, 335, 336, 339, 340, 341, 342, 344, 365, 369, 372, 373, 374, 398, 399, 400, 401, 402, 411, 412, 486, 487, 488, 489, 491, 492, 495 NR.sub.11 N or S or C or 6 183, 204, 307 single bond O O or N or S or C 7 160, 163, 170, 185, 194, 256, 268, 337, 368, 370, 413 or single bond S S or C or single 8 145, 161, 175, 178, 197, 263, 269 bond O CR.sub.9R.sub.10 Single bond or 9 56, 58, 60, 61, 62, 63, 65, 66, 67, 69, 70, 71, 72, 73, 74, carbon atom 76, 77, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 90, 109, 110, group 111, 112, 113, 114, 116, 117, 120, 122, 125, 126, 218, 219, 221, 222, 226, 227, 228, 229, 230, 234, 365, 371, 375, 376, 377, 378, 398, 409, 482, 490, 499 NR.sub.11 N or S or C or 10 57 single bond SiR.sub.12R.sub.13 Si or C or single 11 68 bond O O or N or S or C 12 59, 78, 115, 217 or single bond S S or C or single 13 55, 64, 75, 220, 366, 484 bond S CR.sub.9R.sub.10 Single bond or 14 91, 92, 94, 95, 96, 97, 101, 102, 103, 104, 105, 106, 107, carbon atom 108, 118, 121, 123, 223, 224, 225, 231, 232, 233, 483 group O O or N or S or C 15 93, 98, 99, 100 or single bond BR.sub.8 CR.sub.9R.sub.10 Single bond or 16 343, 344, 345, 347, 349, 350, 351, 353, 354, 356, 357, carbon atom 358, 360, 361, 379, 380, 381, 383, 384, 385, 386, 387, group 389, 390, 391, 392, 393, 394, 395, 396, 397, 400, 5, 406, 407, 408, 414, 416, 418, 420, 421, 422, 423, 425, 426, 427, 429, 430, 431, 432, 433, 434, 436, 437, 439, 440, 441, 442, 444, 445, 446, 447, 448, 449, 450, 496, 497, 498, 500, 501, 502 NR.sub.11 N or S or C or 17 352, 363, 403, 417 single bond SiR.sub.12R.sub.13 Si or C or single 18 428 bond O O or N or S or C 19 348, 359, 362, 382, 388, 419, 438 or single bond S S or C or single 20 346, 355, 404, 415, 424, 435 bond
[0094] The compounds of the present disclosure may form an organic layer with other compounds, and applied in various scenarios. Such an organic layer may be applied in an organic optoelectronic device.
[0095] The compounds of the present disclosure have different triplet energy levels of the molecules due to their different compositions. According to different application scenarios, a suitable energy level may be selected for application in red light devices or green light devices.
[0096] The compounds of the present disclosure have different molecular properties due to different group combinations, and may be used in a green light buffer layer. The so-called green light buffer layer refers to a functional layer that can adjust the migration rate and number of electrons and holes in the device.
[0097] The organic optoelectronic device provided by the present disclosure includes a first electrode, a second electrode, and one or more organic layers arranged between the first electrode and the second electrode. It is in a bottom or top light-emitting structure. The organic layer may be a single-layer structure, or a multi-layer series structure with two or more organic layers laminated together. The organic layer includes at least one of a hole injection layer, a hole transport layer, a light-emitting layer, an electron injection layer or an electron transport layer. The conventional methods and materials for preparing organic optoelectronic devices may be used for preparation of this device. The organic optoelectronic device of the present disclosure uses the compound as the organic layer of the organic optoelectronic device.
[0098] In the organic optoelectronic device provided by the present disclosure, the first electrode serves as an anode layer, and the anode material may be, for example, a material with a large work function, so that holes are smoothly injected into the organic layer. More examples include metals, metal oxides, combinations of metals and oxides, conductive polymers, and the like. The metal oxide may be, for example, indium tin oxide (ITO), zinc oxide, indium oxide, indium zinc oxide (IZO), or the like.
[0099] In the organic optoelectronic device provided by the present disclosure, the second electrode serves as a cathode layer, and the cathode material may be, for example, a material with a small work function, so that electrons are smoothly injected into the organic layer. The cathode material may be, for example, a metal or a multilayer structure material. The metal may be, for example, magnesium, silver, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, tin and lead, or alloys thereof. The cathode material is preferably selected from magnesium and silver.
[0100] In the organic optoelectronic device provided by the present disclosure, the material of the hole injection layer is preferably a material whose highest occupied molecular orbital (HOMO) is between the work function of the anode material and the HOMO of the surrounding organic layer(s), and makes it advantageous for receiving holes from the anode at a low voltage.
[0101] In the organic optoelectronic device provided by the present disclosure, the material of the hole transport layer is a material having high mobility for holes, and is suitable for receiving holes from the anode or the hole injection layer and transporting the holes to the light-emitting layer. The material of the hole transport layer includes, but is not limited to, an organic material of arylamine, a conductive polymer, a block copolymer having both a conjugated part and a non-conjugated part, and the like.
[0102] In the organic optoelectronic device provided by the present disclosure, the material of the light-emitting layer may generally be selected from materials with good quantum efficiency for fluorescence or phosphorescence, and make it possible to emit light in the visible light region by receiving holes and electrons respectively from the hole transport layer and the electron transport layer and combining the holes with the electrons.
[0103] In the organic optoelectronic device provided by the present disclosure, the material of the electron transport layer is a material having high electron mobility, which is suitable for advantageously receiving electrons from the cathode and transporting the electrons to the light-emitting layer.
[0104] In the organic optoelectronic device provided by the present disclosure, the material of a cover layer generally has a high refractive index, and thus can help improve the light efficiency of the organic light-emitting device, especially help improve the external light-emitting efficiency.
[0105] In the organic optoelectronic device provided by the present disclosure, the organic optoelectronic device is an organic photovoltaic device, an organic light-emitting device, an organic solar cell, an electronic paper, an organic photoreceptor, an organic thin film transistor, etc.
[0106] Another aspect of the present disclosure provides a display or lighting device, which includes the organic optoelectronic device of the present disclosure.
[0107] The following describes the embodiments of the present disclosure by means of specific examples.
Synthesis Example
[0108] The compound represented by the above formula (I) may be synthesized by a known method, such as cross-coupling reactions using transition metals such as nickel and palladium. Other synthetic methods are CC, CN coupling reactions using transition metals such as magnesium or zinc. Among the above reactions, Suzuki or Buchwald reaction is preferable due to mild reaction conditions and superior selectivity of various functional groups. The compounds of the present disclosure are illustrated by the following examples, but are not limited to the compounds and synthetic methods exemplified in these examples. The raw materials and solvents of the present disclosure and some commonly used OLED intermediates and other products were purchased from domestic OLED intermediate manufacturers; various palladium catalysts, ligands and the like were purchased from Sigma-Aldrich Company. .sup.1H-NMR data was measured using a JEOL (400 MHz) nuclear magnetic resonance instrument; HPLC data was measured using a Shimadzu LC-20AD high performance liquid chromatography instrument.
Example 1
Synthesis of Compound 1
##STR00208##
1) Synthesis of Intermediate 1-1
[0109] Under an argon atmosphere, 24.4 g (100 mmol) of compound 1-A, 46.6 g (200 mmol) of compound 1-B, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol %) of bis(dibenzylideneacetone)palladium, 953 mg (2 mmol %) of 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl and 1000 mL of xylene were added to a reaction container, and heated to 140 C. with stirring for 15 hours. The reaction mixture was cooled to room temperature, and 1000 ml of water was added thereto. The mixture was filtered. The filter cake was washed with a large amount of water and dried in vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 46.6 g of compound 1-1 with a HPLC purity of 99.5% and a yield of 85%. LC MS: M/Z 547.21 (M+).
[0110] .sup.1H NMR (500 MHz, DMSO-d6) 7.68-7.62 (m, 4H), 7.61-7.55 (m, 5H), 7.52-7.41 (m, 6H), 7.41-7.31 (m, 4H), 7.27-7.22 (m, 4H), 7.04 (s, 1H), 1.60 (s, 6H).
2) Synthesis of Compound 1
[0111] Under an argon atmosphere, 54.8 g (101 mmol) of compound 1-1, 16.2 g (100 mmol) of compound 1-C, 787 mg (1 mmol %) of XPhos Pd G3, 50 ml (300 mmol) of 1.5 M potassium phosphate and 1000 ml of tetrahydrofuran (THF) were added to a reaction container and stirred under reflux overnight. After cooling to room temperature, 800 ml of water was added thereto, and a large amount of solid precipitated. The solid was filtered, and the filter cake was washed with water three times and dried in vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 54.2 g of compound 1 with a yield of 86% and a HPLC purity of 99.9%. LC-MS: M/Z 629.31 (M+).
[0112] .sup.1H NMR (500 MHz, DMSO-d6) 7.81 (s, 1H), 7.69-7.63 (m, 4H), 7.60-7.52 (m, 5H), 7.50-7.40 (m, 6H), 7.40-7.30 (m, 4H), 7.30-7.20 (m, 2H), 7.18-7.12 (m, 4H), 7.03 (s, 1H), 2.88 (m, 2H), 2.80 (t, 2H), 2.20 (m, 2H), 1.58 (s, 6H).
Example 2
Synthesis of Compound 20
##STR00209##
1) Synthesis of Intermediate 20-1
[0113] Under an argon atmosphere, 30.8 g (100 mmol) of compound 20-A, 18.3 g (100 mmol) of compound 20-B, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol %) of bis(dibenzylideneacetone)palladium, 953 mg (2 mmol %) of 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl and 1000 mL of xylene were added to a reaction container, and heated to 140 C. with stirring for 15 hours. The reaction mixture was cooled to room temperature, and 1000 ml of water was added thereto. The mixture was filtered. The filter cake was washed with a large amount of water and dried in vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 32.7 g of compound 20-1 with a HPLC purity of 99.5% and a yield of 80%. LC MS: M/Z 409.12 (M+).
[0114] .sup.1H NMR (500 MHz, DMSO-d6) 9.55 (s, 1H), 8.06-7.98 (m, 2H), 7.67 (s, 1H), 7.59 (m, 1H), 7.54-7.44 (m, 4H), 7.41-7.29 (m, 3H), 6.90 (s, 1H), 6.86 (m, 1H), 1.58 (s, 6H).
2) Synthesis of Intermediate 20-2
[0115] Under an argon atmosphere, 40.9 g (100 mmol) of compound 20-1, 27.3 g (100 mmol) of compound 20-C, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol %) of bis(dibenzylideneacetone)palladium, 953 mg (2 mmol %) of 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl and 1000 mL of xylene were added to a reaction container, and heated to 140 C. with stirring for 15 hours. The reaction mixture was cooled to room temperature, and 1000 ml of water was added thereto. The mixture was filtered. The filter cake was washed with a large amount of water and dried in vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 48.8 g of compound 20-2 with a HPLC purity of 99.5% and a yield of 86%. LC MS: M/Z 567.26 (M+).
[0116] .sup.1H NMR (500 MHz, DMSO-d6) 8.10 (m, 1H), 7.95 (d, 1H), 7.75-7.66 (m, 2H), 7.59-7.52 (m, 3H), 7.52-7.31 (m, 9H), 7.28 (m, 1H), 6.93 (d, 1H), 6.88 (m, 1H), 6.84 (s, 1H), 1.58 (s, 12H).
3) Synthesis of Compound 20
[0117] Under an argon atmosphere, 56.7 g (100 mmol) of compound 20-2, 17.6 g (100 mmol) of compound 20-D, 787 mg (1 mmol %) of XPhos Pd G3, 50 ml (300 mmol) of 1.5 M potassium phosphate and 1000 ml of tetrahydrofuran (THF) were added to a reaction container, and stirred under reflux overnight. After cooling to room temperature, 800 ml of water was added thereto, and a large amount of solid precipitated. The solid was filtered, and the filter cake was washed with water three times and dried in vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 55.1 g of compound 20 with a yield of 79% and a HPLC purity of 99.9%. LC MS: M/Z 697.33 (M+).
[0118] .sup.1H NMR (500 MHz, DMSO-d6) 8.06 (m, 1H), 7.95 (d, 1H), 7.83 (s, 1H), 7.75-7.67 (m, 2H), 7.58-7.51 (m, 2H), 7.51-7.41 (m, 4H), 7.41-7.30 (m, 5H), 7.28 (m, 1H), 7.26-7.17 (m, 2H), 7.08 (d, 1H), 7.04 (s, 1H), 6.93 (d, 1H), 6.88 (m, 1H), 2.79-2.67 (m, 4H), 1.82-1.68 (m, 4H), 1.59 (s, 12H).
Example 3
Synthesis of Compound 39
##STR00210##
[0119] Except that the starting materials were replaced with 39-A, 39-B, 39-C and 39-D, everything else was the same as Example 2. LC MS: M/Z 720.35 (M+). Total yield of synthesis: 52%; HPLC purity: 99.9%.
[0120] .sup.1H NMR (500 MHz, DMSO-d6) 8.10 (m, 1H), 8.04 (d, 1H), 7.82 (m, 1H), 7.78 (m, 1H), 7.73 (m, 1H), 7.64-7.59 (m, 1H), 7.59-7.22 (m, 19H), 7.17 (m, 1H), 7.15-7.09 (m, 1H), 6.86 (d, 1H), 2.97-2.91 (m, 2H), 2.74 (m, 2H), 1.60 (s, 6H), 1.66-1.52 (m, 6H).
Example 4
Synthesis of Compound 58
##STR00211##
[0121] Except that the starting materials were replaced with 58-A, 58-B, 1-B and 58-D, everything else was the same as Example 2. LC MS: M/Z 721.30 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0122] .sup.1H NMR (500 MHz, DMSO-d6) 8.11-8.05 (m, 1H), 7.86 (d, 1H), 7.69-7.63 (m, 2H), 7.60-7.50 (m, 7H), 7.50-7.29 (m, 13H), 7.25-7.18 (m, 1H), 7.18-7.11 (m, 3H), 7.02 (s, 1H), 4.53 (t, 2H), 3.24 (m, 2H), 1.59 (s, 6H).
Example 5
Synthesis of Compound 77
##STR00212##
[0123] Except that the starting materials were replaced with 77-B, 1-B and 77-D, everything else was the same as Example 2. LC MS: M/Z 639.22 (M+). Total yield of synthesis: 53%; HPLC purity: 99.9%.
[0124] .sup.1H NMR (500 MHz, DMSO-d6) 7.71 (m, 1H), 7.69-7.63 (m, 4H), 7.58-7.51 (m, 3H), 7.46-7.41 (m, 1H), 7.44-7.30 (m, 8H), 7.30 (m, 1H), 7.20 (t, 1H), 7.17-7.11 (m, 2H), 7.09 (d, 1H), 6.99 (m, 1H), 6.83 (d, 1H), 6.34 (d, 1H), 6.09 (s, 2H), 1.60 (s, 6H).
Example 6
Synthesis of Compound 96
##STR00213##
[0125] Except that the starting materials were replaced with 96-B, 1-B and 96-D, everything else was the same as Example 2. LC MS: M/Z 820.26 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%.
[0126] .sup.1H NMR (500 MHz, DMSO-d6) 8.13 (m,1H), 7.81 (d, 1H), 7.75-7.69 (m, 1H), 7.71-7.64 (m, 3H), 7.64-7.57 (m, 3H), 7.57-7.21 (m, 19H), 7.19 (m, 1H), 7.06 (d, 1H), 6.99 (d, 1H), 6.79 (d, 1H), 4.11 (s, 2H), 1.60 (s, 6H).
Example 7
Synthesis of Compound 115
##STR00214##
[0127] Except that the starting materials were replaced with 115-B, 1-B and 115-D, everything else was the same as Example 2. LC MS: M/Z 792.24 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0128] .sup.1H NMR (500 MHz, DMSO-d6) 8.30 (m, 1H), 8.07 (d, 1H), 8.04-7.97 (m, 1H), 7.95 (m, 2H), 7.81 (m, 1H), 7.69-7.63 (m, 2H), 7.62-7.32 (m, 17H), 7.22-7.16 (m, 2H), 7.13 (t, 1H), 7.00 (m, 1H), 6.94 (d, 1H), 6.58 (d, 1H), 5.88 (d, 1H), 4.34-4.24 (m, 4H).
Example 8
Synthesis of Compound 134
##STR00215##
[0129] Except that the starting materials were replaced with 134-A, 134-B, 1-B and 134-D, everything else was the same as Example 2. LC MS: M/Z 723.35 (M+). Total yield of synthesis: 45%; HPLC purity: 99.9%.
[0130] .sup.1H NMR (500 MHz, DMSO-d6) 8.13 (m, 1H), 8.01 (s, 1H), 7.82 (m, 1H), 7.69-7.63 (m, 2H), 7.63-7.58 (m, 2H), 7.58-7.51 (m, 5H), 7.51-7.26 (m, 9H), 7.18-7.08 (m, 4H), 1.85-1.78 (m, 2H), 1.78-1.71 (m, 2H), 1.31 (s, 4H), 0.94 (s, 12H).
Example 9
Synthesis of Compound 153
##STR00216##
[0131] Except that the starting materials were replaced with 58-A, 153-B and 153-D, everything else was the same as Example 2. LC MS: M/Z 730.33 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%.
[0132] .sup.1H NMR (500 MHz, DMSO-d6) 8.06-8.01 (m, 1H), 7.98 (m, 1H), 7.92-7.84 (m, 3H), 7.78 (m, 1H), 7.69-7.63 (m, 2H), 7.61 (m, 1H), 7.58-7.49 (m, 4H), 7.49-7.27 (m, 12H), 7.15 (m, 4H), 7.13-7.05 (m, 2H), 7.01 (s, 1H), 4.12 (t, 2H), 3.17 (m, 1H), 3.09 (m, 1H), 1.59 (s, 6H).
Example 10
Synthesis of Compound 172
##STR00217##
[0133] Except that the starting materials were replaced with 172-B and 172-D, everything else was the same as Example 2. LC MS: M/Z 831.36 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0134] .sup.1H NMR (500 MHz, DMSO-d6) 8.32-8.25 (m, 1H), 8.06 (m, 1H), 8.06-7.99 (m, 2H), 7.91 (m, 1H), 7.76 (m, 1H), 7.73-7.63 (m, 5H), 7.57-7.52 (m, 2H), 7.50 (m, 1H), 7.46-7.33 (m, 10H), 7.36-7.27 (m, 3H), 7.27-7.07 (m, 9H), 6.86 (d, 1H), 4.69 (s, 2H), 1.60 (s, 6H).
Example 11
Synthesis of Compound 191
##STR00218##
[0135] Except that the starting materials were replaced with 191-A and 191-B, everything else was the same as Example 1. LC MS: M/Z 727.36 (M+). Total yield of synthesis: 45%; HPLC purity: 99.9%.
[0136] .sup.1H NMR (500 MHz, DMSO-d6) 7.73 (m, 1H), 7.71-7.63 (m, 3H), 7.61 (t, 1H), 7.57-7.52 (m, 2H), 7.52-7.38 (m, 7H), 7.41-7.31 (m, 2H), 7.23 (t, 1H), 7.20-7.13 (m, 5H), 7.12-6.99 (m, 3H), 6.85 (d, 1H), 3.64 (t, 2H), 2.99 (s, 3H), 2.98 (m, 2H), 1.61 (d, 12H).
Example 12
Synthesis of Compound 210
##STR00219##
[0137] Except that the starting materials were replaced with 39-B, 210-B and 210-D, everything else was the same as Example 2. LC MS: M/Z 763.39 (M+). Total yield of synthesis: 45%; HPLC purity: 99.9%.
[0138] .sup.1H NMR (500 MHz, DMSO-d6) 8.12 (m, 2H), 7.85-7.75 (m, 2H), 7.71 (m, 1H), 7.62 (m, 2H), 7.60-7.54 (m, 1H), 7.51-7.24 (m, 17H), 7.21-7.12 (m, 4H), 7.08 (m, 1H), 6.88 (d, 1H), 3.41 (t, 2H), 2.79 (m, 2H), 1.90 (m, 2H), 1.60 (s, 6H), 1.33 (s, 6H).
Example 13
Synthesis of Compound 229
##STR00220##
[0139] Except that the starting materials were replaced with 229-B, 229-C and 229-D, everything else was the same as Example 2. LC MS: M/Z 660.31 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%.
[0140] .sup.1H NMR (500 MHz, DMSO-d6) 8.17-8.11 (m, 4H), 7.72 (m, 1H), 7.55-7.49 (m, 4H), 7.52-7.24 (m, 12H), 7.22 (d, 1H), 7.18-7.12 (m, 2H), 7.15-7.07 (m, 1H), 6.89 (m, 1H), 3.96 (t, 2H), 2.99 (t, 1H), 2.89 (t, 1H), 1.78 (m, 2H), 1.69 (m, 2H), 1.59 (s, 6H).
Example 14
Synthesis of Compound 248
##STR00221##
[0141] Except that the starting materials were replaced with 58-A, 248-B, 248-C and 248-D, everything else was the same as Example 2. LC MS: M/Z 722.33 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 15
Synthesis of Compound 267
##STR00222##
[0142] Except that the starting materials were replaced with 58-A, 267-B, 248-C and 267-D, everything else was the same as Example 2. LC MS: M/Z 791.42 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0143] .sup.1H NMR (500 MHz, DMSO-d6) 7.71 (m, 1H), 7.60 (m, 1H), 7.56-7.48 (m, 3H), 7.46 (t, 1H), 7.43-7.19 (m, 16H), 7.19-7.11 (m, 2H), 6.98 (m, 4H), 6.91 (m, 2H), 6.73 (t, 1H), 6.55 (m, 1H), 4.60-4.56 (m, 2H), 4.50 (s, 2H), 1.59 (s, 6H).
Example 16
Synthesis of Compound 286
##STR00223##
[0144] Except that the starting materials were replaced with 286-A, 39-B, 286-C and 286-D, everything else was the same as Example 2. LC MS: M/Z 721.30 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0145] .sup.1H NMR (500 MHz, DMSO-d6) 8.02 (m, 2H), 7.90 (m, 2H), 7.86-7.75 (m, 3H), 7.72 (d, 1H), 7.61-7.54 (m, 3H), 7.54-7.41 (m, 4H), 7.39-7.30 (m, 3H), 7.33-7.25 (m, 2H), 7.11-7.04 (m, 2H), 6.96 (d, 1H), 4.16-4.03 (m, 4H), 2.87 (m, 4H), 2.77 (t, 4H), 2.19 (m, 4H).
Example 17
Synthesis of Compound 305
##STR00224##
[0146] Except that the starting materials were replaced with 58-A, 305-B, 1-B and 305-D, everything else was the same as Example 2. LC MS: M/Z 795.39 (M+). Total yield of synthesis: 54%; HPLC purity: 99.9%.
[0147] .sup.1H NMR (500 MHz, DMSO-d6) 8.33 (m, 1H), 8.19 (m, 2H), 7.80-7.63 (m, 7H), 7.58-7.44 (m, 7H), 7.44-7.28 (m, 5H), 7.25 (d, 1H), 7.21-7.15 (m, 2H), 7.11 (t, 1H), 7.07 (s, 1H), 2.98-2.90 (m, 2H), 2.83-2.73 (m, 4H), 2.71 (m, 2H), 1.82-1.68 (m, 8H), 1.59 (s, 6H).
Example 18
Synthesis of Compound 324
##STR00225##
[0148] Except that the starting materials were replaced with 58-A, 324-B, 324-C and 324-D, everything else was the same as Example 1. LC MS: M/Z 935.42 (M+). Total yield of synthesis: 51%; HPLC purity: 99.9%.
[0149] .sup.1H NMR (500 MHz, DMSO-d6) 8.33 (m, 1H), 8.21 (m, 1H), 8.17 (m, 1H), 7.75-7.66 (m, 8H), 7.58-7.43 (m, 7H), 7.40-7.22 (m, 11H), 7.21-7.13 (m, 5H), 7.09 (m, 3H), 7.00 (s, 1H), 6.96 (d, 1H), 4.07 (s, 3H), 4.07 (d, 1H), 1.59 (s, 10H).
Example 19
Synthesis of Compound 343
##STR00226##
[0150] Except that the starting material was replaced with 343-C, everything else was the same as Example 1. LC MS: M/Z 703.34 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%.
[0151] .sup.1H NMR (500 MHz, DMSO-d6) 7.74-7.63 (m, 7H), 7.58-7.49 (m, 6H), 7.49-7.44 (m, 2H), 7.44-7.28 (m, 11H), 7.18 (t, 1H), 7.14-7.08 (m, 4H), 7.06 (s, 1H), 2.81 (m, 1H), 2.65 (t, 2H), 1.94 (t, 1H), 1.59 (s, 6H).
Example 20
Synthesis of Compound 362
##STR00227##
[0152] Except that the starting materials were replaced with 134-A, 20-B, and 362D, everything else was the same as Example 13. LC MS: M/Z 729.27 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0153] .sup.1H NMR (500 MHz, DMSO-d6) 8.09-8.04 (m, 1H), 8.03 (d, 2H), 7.91 (d, 1H), 7.79 (d, 1H), 7.76-7.66 (m, 7H), 7.58-7.52 (m, 2H), 7.51-7.41 (m, 6H), 7.41-7.31 (m, 6H), 7.34-7.29 (m, 3H), 7.25 (m, 1H), 7.08 (d, 1H), 6.97 (d, 1H), 6.88 (m, 1H), 3.28 (s, 2H), 1.59 (s, 6H).
Example 21
Synthesis of Compound 381
##STR00228##
[0154] Except that the starting materials were replaced with 39-C and 381-D, everything else was the same as Example 2. LC MS: M/Z 768.77 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%.
[0155] .sup.1H NMR (500 MHz, DMSO-d6) 8.10 (m, 1H), 8.04 (d, 1H), 7.85-7.80 (m, 1H), 7.80-7.72 (m, 3H), 7.69 (m, 1H), 7.62 (m, 1H), 7.59-7.45 (m, 5H), 7.47-7.42 (m, 2H), 7.45-7.33 (m, 5H), 7.35 (d, 3H), 7.36-7.30 (m, 2H), 7.33-7.25 (m, 4H), 7.27-7.20 (m, 2H), 7.18 (m, 1H), 7.09 (d, 1H), 3.44 (d, 2H), 1.60 (s, 6H).
Example 22
Synthesis of Compound 400
##STR00229##
[0156] Except that the starting materials were replaced with 1-A, 1-B, 400-C and 400-D, everything else was the same as Example 2. LC MS: M/Z 826.36 (M+). Total yield of synthesis: 51%; HPLC purity: 99.9%.
[0157] .sup.1H NMR (500 MHz, DMSO-d6) 8.03 (m, 1H), 7.84 (d, 1H), 7.69-7.63 (m, 2H), 7.60-7.50 (m, 7H), 7.50-7.42 (m, 5H), 7.44-7.39 (m, 2H), 7.42-7.32 (m, 5H), 7.35-7.28 (m, 1H), 7.31-7.25 (m, 1H), 7.28-7.21 (m, 2H), 7.14 (m, 3H), 7.02 (s, 1H), 6.98-6.92 (m, 2H), 6.91 (m, 1H), 4.57 (d, 2H), 4.18 (t, 2H), 3.63 (t, 2H), 1.59 (s, 6H).
Example 23
Synthesis of Compound 419
##STR00230##
[0158] Except that the starting materials were replaced with 419-B, 1-B and 419-D, everything else was the same as Example 2. LC MS: M/Z 685.22 (M+). Total yield of synthesis: 53%; HPLC purity: 99.9%.
[0159] .sup.1H NMR (500 MHz, DMSO-d6) 8.04-7.96 (m, 2H), 7.74-7.68 (m, 2H), 7.66 (m, 4H), 7.61-7.53 (m, 5H), 7.48-7.27 (m, 12H), 7.17-7.11 (m, 2H), 6.98 (d, 1H), 6.83 (d, 1H), 6.34 (d, 1H), 5.14 (d, 2H).
Example 24
Synthesis of Compound 438
##STR00231##
[0160] Except that the starting materials were replaced with 438-A, 438-B, 1-B and 438-D, everything else was the same as Example 2. LC MS: M/Z 642.23 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0161] .sup.1H NMR (500 MHz, DMSO-d6) 8.13 (m, 1H), 8.06 (m, 1H), 7.91 (d, 1H), 7.84 (d, 1H), 7.71 (d, 1H), 7.69-7.39 (m, 17H), 7.39-7.32 (m, 1H), 7.32-7.24 (m, 4H), 7.19 (m, 1H), 7.06 (d, 1H), 6.73 (d, 1H).
Example 25
Synthesis of Compound 449
##STR00232##
[0162] Except that the starting materials were replaced with 58-A, 305-B, 1-B and 449-D, everything else was the same as Example 2. LC MS: M/Z 892.40 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0163] .sup.1H NMR (500 MHz, DMSO-d6) 8.33 (m, 1H), 8.21 (m, 1H), 8.17 (m, 1H), 7.78 (s, 1H), 7.75-7.63 (m, 8H), 7.58-7.44 (m, 7H), 7.44-7.25 (m, 13H), 7.25-7.16 (m, 4H), 7.15 (m, 1H), 7.10 (m, 1H), 7.03 (s, 1H), 3.97 (t, 2H), 2.66 (t, 2H), 1.59 (s, 6H).
Example 26
Synthesis of Compound 2
##STR00233##
[0164] Except that the starting materials were replaced with 2-A, 2-B, 2-C and 2-D, everything else was the same as Example 2. LC MS: M/Z 657.27 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0165] .sup.1H NMR (500 MHz, DMSO-d6) 8.16 (m, 1H), 8.06 (m, 1H), 8.00 (s, 1H), 7.92 (d, 1H), 7.76-7.68 (m, 2H), 7.55 (m, 2H), 7.52-7.40 (m, 6H), 7.40-7.27 (m, 5H), 7.24 (m, 1H), 7.10 (d, 1H), 6.93 (d, 1H), 6.88 (m, 1H), 2.92-2.84 (m, 4H), 2.14 (m, 2H), 1.58 (s, 6H).
Example 27
Synthesis of Compound 8
##STR00234##
[0166] Except that the starting materials were replaced with 8-A, 8-B, 8-C and 8-D, everything else was the same as Example 2. LC MS: M/Z 709.30 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0167] .sup.1H NMR (500 MHz, DMSO-d6) 7.82 (m, 1H), 7.74-7.68 (m, 2H), 7.68-7.63 (m, 2H), 7.63-7.58 (m, 2H), 7.58-7.51 (m, 4H), 7.45-7.35 (m, 7H), 7.35 (m, 4H), 7.35-7.24 (m, 2H), 7.28-7.20 (m, 2H), 7.19-7.12 (m, 3H), 4.11 (s, 4H), 2.92-2.85 (m, 2H), 2.78 (t, 2H), 2.18 (m, 2H).
Example 28
Synthesis of Compound 11
##STR00235##
[0168] Except that the starting materials were replaced with 11-A, 11-B, 11-C and 11-D, everything else was the same as Example 2. LC MS: M/Z 698.29 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0169] .sup.1H NMR (500 MHz, DMSO-d6) 7.75 (m, 1H), 7.73-7.63 (m, 3H), 7.62 (t, 1H), 7.58-7.53 (m, 2H), 7.53-7.24 (m, 15H), 7.21-7.13 (m, 3H), 6.87 (d, 1H), 4.22-4.16 (m, 1H), 4.16-4.09 (m, 1H), 3.91 (t, 2H), 2.95-2.80 (m, 2H), 2.78-2.69 (m, 2H), 2.72-2.55 (m, 2H), 2.25-2.08 (m, 2H).
Example 29
Synthesis of Compound 128
##STR00236##
[0170] Except that the starting material was replaced with 128-D, everything else was the same as Example 2. LC MS: M/Z 697.33 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0171] .sup.1H NMR (500 MHz, DMSO-d6) 8.06 (m, 1H), 7.95 (d, 1H), 7.83 (s, 1H), 7.75-7.67 (m, 2H), 7.58-7.51 (m, 2H), 7.51-7.41 (m, 4H), 7.41-7.30 (m, 5H), 7.28 (m, 1H), 7.26-7.17 (m, 2H), 7.08 (d, 1H), 7.04 (s, 1H), 6.93 (d, 1H), 6.88 (m, 1H), 2.79-2.67 (m, 4H), 1.82-1.68 (m, 4H), 1.59 (s, 12H).
Example 30
Synthesis of Compound 130
##STR00237##
[0172] Except that the starting materials were replaced with 130-B, 130-C and 130-D, everything else was the same as Example 2. LC MS: M/Z 789.40 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0173] .sup.1H NMR (500 MHz, DMSO-d6) 8.07-8.01 (m, 1H), 7.84 (d, 1H), 7.69-7.63 (m, 2H), 7.60-7.29 (m, 15H), 7.25 (t, 1H), 7.18-7.09 (m, 4H), 7.08 (s, 1H), 1.85-1.78 (m, 2H), 1.78-1.71 (m, 2H), 1.59 (s, 6H), 1.32 (s, 4H), 1.29 (s, 12H).
Example 31
Synthesis of Compound 137
##STR00238##
[0174] Except that the starting materials were replaced with 137-B, 137-C and 137-D, everything else was the same as Example 2. LC MS: M/Z 740.38 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0175] .sup.1H NMR (500 MHz, DMSO-d6) 7.76 (m, 1H), 7.72-7.63 (m, 3H), 7.61 (t, 1H), 7.58-7.51 (m, 2H), 7.54-7.27 (m, 10H), 7.20-7.12 (m, 4H), 6.91 (d, 1H), 1.83-1.71 (m, 4H), 1.60 (s, 6H), 1.32 (s, 4H), 1.29 (s, 12H).
Example 32
Synthesis of Compound 139
##STR00239##
[0176] Except that the starting materials were replaced with 139-A, 139-B, 139-C and 139-D, everything else was the same as Example 2. LC MS: M/Z 700.38 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0177] .sup.1H NMR (500 MHz, DMSO-d6) 8.17-8.10 (m, 4H), 7.75 (m, 1H), 7.56-7.48 (m, 4H), 7.48-7.24 (m, 8H), 7.17-7.04 (m, 5H), 1.81-1.70 (m, 4H), 1.59 (s, 6H), 1.31 (s, 4H), 1.28 (s, 12H).
Example 33
Synthesis of Compound 451
##STR00240##
[0178] Except that the starting materials were replaced with 451-A and 451-C, everything else was the same as Example 1. LC MS: M/Z 719.44 (M+). Total yield of synthesis: 59%; HPLC purity: 99.9%.
[0179] .sup.1H NMR (500 MHz, DMSO-d6) 7.87 (s, 1H), 7.69-7.63 (m, 4H), 7.57-7.50 (m, 6H), 7.47 (m, 2H), 7.44-7.32 (m, 6H), 7.29 (m, 1H), 7.20-7.12 (m, 6H), 7.04 (d, 1H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 34
Synthesis of Compound 452
##STR00241##
[0180] Except that the starting materials were replaced with 452-A, 452-B, 452-C and 452-D, everything else was the same as Example 2. LC MS: M/Z 892.40 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0181] .sup.1H NMR (500 MHz, DMSO-d6) 7.86 (s, 1H), 7.72 (m, 1H), 7.69-7.61 (m, 3H), 7.58-7.50 (m, 3H), 7.49-7.27 (m, 11H), 7.25 (m, 1H), 7.22-7.12 (m, 4H), 6.99 (d, 1H), 1.74 (s, 3H), 1.74 (d, J=1H), 1.28 (d, 12H).
Example 35
Synthesis of Compound 456
##STR00242##
[0182] Except that the starting materials were replaced with 456-A and 456-C, everything else was the same as Example 2. LC MS: M/Z 837.43 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0183] .sup.1H NMR (500 MHz, DMSO-d6) 7.85 (s, 1H), 7.69-7.63 (m, 4H), 7.59 (m, 1H), 7.57-7.51 (m, 4H), 7.49-7.32 (m, 8H), 7.32-7.19 (m, 7H), 7.18-7.10 (m, 10H), 7.05-7.00 (m, 2H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 36
Synthesis of Compound 457
##STR00243##
[0184] Except that the starting materials were replaced with 456-A and 457-C, everything else was the same as Example 2. LC MS: M/Z 823.42 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0185] .sup.1H NMR (500 MHz, DMSO-d6) 7.85 (s, 1H), 7.69-7.63 (m, 4H), 7.59 (m, 1H), 7.57-7.51 (m, 4H), 7.46-7.37 (m, 6H), 7.40-7.32 (m, 4H), 7.32-7.09 (m, 13H), 7.02 (s, 1H), 1.74 (s, 3H), 1.38 (s, 4H), 0.98 (s, 12H).
Example 37
Synthesis of Compound 458
##STR00244##
[0186] Except that the starting materials were replaced with 458-A and 456-C, everything else was the same as Example 2. LC MS: M/Z 892.40 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0187] .sup.1H NMR (500 MHz, DMSO-d6) 7.84 (m, 2H), 7.81 (s, 1H), 7.69-7.63 (m, 4H), 7.59 (m, 1H), 7.57-7.51 (m, 4H), 7.46 (m, 1H), 7.44-7.25 (m, 12H), 7.18-7.12 (m, 5H), 7.06-7.01 (m, 2H), 6.87 (m, 1H), 6.83-6.78 (m, 2H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 38
Synthesis of Compound 461
##STR00245##
[0188] Except that the starting materials were replaced with 461-B and 456-C, everything else was the same as Example 2. LC MS: M/Z 753.43 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0189] .sup.1H NMR (500 MHz, DMSO-d6) 7.87 (s, 1H), 7.75-7.63 (m, 4H), 7.57-7.50 (m, 3H), 7.47 (m, 3H), 7.44-7.39 (m, 1H), 7.42-7.30 (m, 6H), 7.23 (m, 1H), 7.18-7.12 (m, 3H), 7.09 (s, 1H), 7.04 (d, 1H), 6.97 (d, 1H), 1.59 (d, 12H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 39
Synthesis of Compound 462
##STR00246##
[0190] Except that the starting materials were replaced with 462-C and 462-D, everything else was the same as Example 2. LC MS: M/Z 713.37 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0191] .sup.1H NMR (500 MHz, DMSO-d6) 8.01 (m, 1H), 7.94 (d, 1H), 7.85 (s, 1H), 7.69-7.63 (m, 2H), 7.58-7.50 (m, 4H), 7.52-7.29 (m, 10H), 7.22-7.12 (m, 3H), 7.11-7.05 (m, 2H), 6.88 (m, 1H), 1.74 (s, 4H), 1.59 (s, 6H), 1.28 (d, 12H).
Example 40
Synthesis of Compound 464
##STR00247##
[0192] Except that the starting materials were replaced with 464-B, 464-C and 464-D, everything else was the same as Example 2. LC MS: M/Z 915.48 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0193] .sup.1H NMR (500 MHz, DMSO-d6) 7.89-7.82 (m, 4H), 7.75-7.66 (m, 3H), 7.53 (m, 1H), 7.49-7.43 (m, 3H), 7.40-7.20 (m, 12H), 7.15 (d, 1H), 7.09 (s, 1H), 7.03 (d, 1H), 6.95 (d, 1H), 6.85 (d, 1H), 6.81 (m, 1H), 6.75 (m, 2H), 1.59 (s, 12H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 41
Synthesis of Compound 465
##STR00248##
[0194] Except that the starting materials were replaced with 465-B, 465-C and 465-D, everything else was the same as Example 2. LC MS: M/Z 953.50 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0195] .sup.1H NMR (500 MHz, DMSO-d6) 7.85 (s, 1H), 7.81 (d, 1H), 7.72 (m, 1H), 7.69-7.63 (m, 2H), 7.63-7.51 (m, 9H), 7.46 (m, 1H), 7.45-7.40 (m, 4H), 7.43-7.35 (m, 6H), 7.38-7.31 (m, 4H), 7.33-7.25 (m, 5H), 7.28-7.19 (m, 3H), 7.21-7.13 (m, 5H), 7.16-7.10 (m, 5H), 7.05-7.00 (m, 2H), 1.59 (s, 6H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 42
Synthesis of Compound 467
##STR00249##
[0196] Except that the starting materials were replaced with 467-A, 467-B, 467-C and 467-D, everything else was the same as Example 2. LC MS: M/Z 911.41 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0197] .sup.1H NMR (500 MHz, DMSO-d6) 8.06-8.00 (m, 1H), 7.89 (d, 1H), 7.84 (m, 2H), 7.81 (s, 1H), 7.73 (d, 1H), 7.69-7.63 (m, 2H), 7.65-7.59 (m, 2H), 7.63-7.44 (m, 6H), 7.48-7.33 (m, 6H), 7.36-7.25 (m, 6H), 7.19 (d, 1H), 7.17-7.12 (m, 4H), 7.04 (s, 1H), 6.87 (m, 1H), 6.84-6.77 (m, 2H), 1.74 (s, 4H), 1.28 (s, 12H).
Example 43
Synthesis of Compound 469
##STR00250## ##STR00251##
[0198] Except that the starting materials were replaced with 469-B, 469-C and 467-D, everything else was the same as Example 2. LC MS: M/Z 892.40 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0199] .sup.1H NMR (500 MHz, DMSO-d6) 7.92 (d, 1H), 7.89-7.82 (m, 2H), 7.73 (d, 1H), 7.69-7.57 (m, 5H), 7.57-7.50 (m, 3H), 7.50-7.28 (m, 11H), 7.22-7.12 (m, 3H), 7.16-7.07 (m, 2H), 6.89 (m, 1H), 1.74 (s, 3H), 1.74 (d, 1H), 1.59 (s, 6H), 1.28 (s, 12H).
Example 44
Synthesis of Compound 470
##STR00252##
[0200] Except that the starting materials were replaced with 470-B, 470-C and 470-D, everything else was the same as Example 2. LC MS: M/Z 803.38 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0201] .sup.1H NMR (500 MHz, DMSO-d6) 8.07-8.00 (m, 2H), 7.92 (d, 1H), 7.90-7.85 (m, 2H), 7.67-7.59 (m, 3H), 7.59-7.51 (m, 3H), 7.54-7.47 (m, 1H), 7.51-7.40 (m, 6H), 7.40-7.33 (m, 2H), 7.32 (m, 1H), 7.22-7.13 (m, 3H), 7.11-7.05 (m, 2H), 6.88 (m, 1H), 1.74 (s, 3H), 1.74 (d, 1H), 1.59 (s, 6H), 1.28 (s, 12H).
Example 45
Synthesis of Compound 471
##STR00253##
[0202] Except that the starting materials were replaced with 470-B, 471-C and 471-D, everything else was the same as Example 2. LC MS: M/Z 803.38 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0203] .sup.1H NMR (500 MHz, DMSO-d6) 8.03 (m, 1H), 7.92 (d, 1H), 7.87 (s, 1H), 7.69-7.59 (m, 2H), 7.63 (s, 4H), 7.58-7.51 (m, 4H), 7.51-7.28 (m, 10H), 7.22-7.12 (m, 3H), 7.11-7.05 (m, 2H), 6.88 (m, 1H), 1.74 (s, 3H), 1.74 (d, 1H), 1.59 (s, 6H), 1.28 (s, 12H).
Example 46
Synthesis of Compound 473
##STR00254##
[0204] Except that the starting materials were replaced with 473-A, 473-B, 473-C and 473-D, everything else was the same as Example 2. LC MS: M/Z 851.41 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0205] .sup.1H NMR (500 MHz, DMSO-d6) 8.01 (m, 1H), 7.92 (d, 1H), 7.73 (m, 1H), 7.69-7.63 (m, 2H), 7.59-7.52 (m, 3H), 7.51-7.32 (m, 8H), 7.32-7.20 (m, 8H), 7.20-7.13 (m, 4H), 7.13-7.06 (m, 5H), 7.03 (d, 1H), 6.87 (m, 1H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 47
Synthesis of Compound 475
##STR00255## ##STR00256##
[0206] Except that the starting materials were replaced with 475-A, 475-B, 475-C and 475-D, everything else was the same as Example 2. LC MS: M/Z 911.41 (M+). Total yield of synthesis: 45%; HPLC purity: 99.9%.
[0207] .sup.1H NMR (500 MHz, DMSO-d6) 7.92 (d, 1H), 7.84 (m, 3H), 7.73 (d, 1H), 7.71-7.59 (m, 5H), 7.59-7.51 (m, 3H), 7.49 (m, 1H), 7.45-7.35 (m, 6H), 7.39-7.30 (m, 4H), 7.33-7.23 (m, 6H), 7.21 (d, 1H), 7.18-7.09 (m, 3H), 6.89 (m, 1H), 6.81 (m, 2H), 1.74 (s, 3H), 1.74 (d, 1H), 1.28 (d, 12H).
Example 48
Synthesis of Compound 477
##STR00257##
[0208] Except that the starting materials were replaced with 477-A, 477-B, 477-C and 477-D, everything else was the same as Example 2. LC MS: M/Z 809.45 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0209] .sup.1H NMR (500 MHz, DMSO-d6) 7.93 (d, 1H), 7.84 (d, 1H), 7.77-7.71 (m, 2H), 7.69-7.54 (m, 8H), 7.49-7.42 (m, 3H), 7.45-7.39 (m, 1H), 7.42-7.35 (m, 4H), 7.38-7.30 (m, 1H), 7.32-7.25 (m, 2H), 7.17 (m, 2H), 7.09 (d, 1H), 7.04 (d, 1H), 6.95 (d, 1H), 6.88 (m, 1H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 49
Synthesis of Compound 3
##STR00258##
[0210] Except that the starting materials were replaced with 3-A, 3-B, 3-C and 3-D, everything else was the same as Example 2. LC MS: M/Z 741.31 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0211] .sup.1H NMR (500 MHz, DMSO-d6) 8.10 (m, 1H), 8.05 (d, 1H), 7.98-7.90 (m, 1H), 7.80 (m, 2H), 7.65-7.40 (m, 16H), 7.38-7.16 (m, 11H), 7.11 (d, 1H), 2.92-2.85 (m, 2H), 2.72 (t, 2H), 2.17 (m, 2H).
Example 50
Synthesis of Compound 6
##STR00259##
[0212] Except that the starting materials were replaced with 6-A, 6-B, 6-C and 6-D, everything else was the same as Example 2. LC MS: M/Z 774.27 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 51
Synthesis of Compound 28
##STR00260##
[0213] Except that the starting materials were replaced with 28-A, 28-B, 28-C and 28-D, everything else was the same as Example 2. LC MS: M/Z 809.45 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 52
Synthesis of Compound 43
##STR00261##
[0214] Except that the starting materials were replaced with 43-A, 43-B, 43-C and 43-D, everything else was the same as Example 2. LC MS: M/Z 968.39 (M+). Total yield of synthesis: 45%; HPLC purity: 99.9%.
Example 53
Synthesis of Compound 44
##STR00262##
[0215] Except that the starting materials were replaced with 44-A, 44-B, 44-C and 44-D, everything else was the same as Example 2. LC MS: M/Z 729.25 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 54
Synthesis of Compound 55
##STR00263##
[0216] Except that the starting materials were replaced with 55-A, 55-B, 55-C and 55-D, everything else was the same as Example 2. LC MS: M/Z 621.21 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 55
Synthesis of Compound 57
##STR00264##
[0217] Except that the starting materials were replaced with 57-A, 57-B, 57-C and 57-D, everything else was the same as Example 2. LC MS: M/Z 743.29 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 56
Synthesis of Compound 64
##STR00265##
[0218] Except that the starting materials were replaced with 64-A, 64-B, 64-C and 64-D, everything else was the same as Example 2. LC MS: M/Z 697.24 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 57
Synthesis of Compound 68
##STR00266##
[0219] Except that the starting materials were replaced with 68-A, 68-B, 68-C and 68-D, everything else was the same as Example 2. LC MS: M/Z 663.26 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 58
Synthesis of Compound 93
##STR00267##
[0220] Except that the starting materials were replaced with 93-A, 93-B, 93-C and 93-D, everything else was the same as Example 2. LC MS: M/Z 700.20 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 59
Synthesis of Compound 98
##STR00268##
[0221] Except that the starting materials were replaced with 98-A, 98-B, 98-C and 98-D, everything else was the same as Example 2. LC MS: M/Z 671.23 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 60
Synthesis of Compound 100
##STR00269##
[0222] Except that the starting materials were replaced with 100-A, 100-B, 100-C and 100-D, everything else was the same as Example 2. LC MS: M/Z 760.25 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 61
Synthesis of Compound 127
##STR00270##
[0223] Except that the starting materials were replaced with 127-A, 127-B, 127-C and 127-D, everything else was the same as Example 2. LC MS: M/Z 748.38 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 62
Synthesis of Compound 145
##STR00271##
[0224] Except that the starting materials were replaced with 145-A, 145-B, 145-C and 145-D, everything else was the same as Example 2. LC MS: M/Z 696.26 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
Example 63
Synthesis of Compound 160
##STR00272##
[0225] Except that the starting materials were replaced with 160-A, 160-B, 160-C and 160-D, everything else was the same as Example 2. LC MS: M/Z 702.27 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 64
Synthesis of Compound 161
##STR00273##
[0226] Except that the starting materials were replaced with 161-A, 161-B, 161-C and 161-D, everything else was the same as Example 2. LC MS: M/Z 794.28 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 65
Synthesis of Compound 170
##STR00274##
[0227] Except that the starting materials were replaced with 170-A, 170-B, 170-C and 170-D, everything else was the same as Example 2. LC MS: M/Z 807.32 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 66
Synthesis of Compound 175
##STR00275##
[0228] Except that the starting materials were replaced with 175-A, 175-B, 175-C and 175-D, everything else was the same as Example 2. LC MS: M/Z 774.28 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 67
Synthesis of Compound 183
##STR00276##
[0229] Except that the starting materials were replaced with 183-A, 183-B, 183-C and 183-D, everything else was the same as Example 2. LC MS: M/Z 756.33 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 68
Synthesis of Compound 204
##STR00277##
[0230] Except that the starting materials were replaced with 204-A, 204-B, 204-C and 204-D, everything else was the same as Example 2. LC MS: M/Z 924.38 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 69
Synthesis of Compound 220
##STR00278##
[0231] Except that the starting materials were replaced with 220-A, 220-B, 220-C and 220-D, everything else was the same as Example 2. LC MS: M/Z 739.25 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 70
Synthesis of Compound 256
##STR00279##
[0232] Except that the starting materials were replaced with 256-A, 256-B, 256-C and 256-D, everything else was the same as Example 2. LC MS: M/Z 784.31 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 71
Synthesis of Compound 293
##STR00280##
[0233] Except that the starting materials were replaced with 293-A, 293-B, 293-C and 293-D, everything else was the same as Example 2. LC MS: M/Z 809.45 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 72
Synthesis of Compound 305
##STR00281##
[0234] Except that the starting materials were replaced with 305-A, 305-B, 305-C and 305-D, everything else was the same as Example 2. LC MS: M/Z 795.39 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 73
Synthesis of Compound 307
##STR00282##
[0235] Except that the starting materials were replaced with 307-A, 307-B, 307-C and 307-D, everything else was the same as Example 2. LC MS: M/Z 846.37 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 74
Synthesis of Compound 352
##STR00283##
[0236] Except that the starting materials were replaced with 352-A, 352-B, 352-C and 352-D, everything else was the same as Example 2. LC MS: M/Z 814.35 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 75
Synthesis of Compound 355
##STR00284##
[0237] Except that the starting materials were replaced with 355-A, 355-B, 355-C and 355-D, everything else was the same as Example 2. LC MS: M/Z 722.29 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
Example 76
Synthesis of Compound 363
##STR00285##
[0238] Except that the starting materials were replaced with 363-A, 363-B, 363-C and 363-D, everything else was the same as Example 2. LC MS: M/Z 889.38 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 77
Synthesis of Compound 391
##STR00286##
[0239] Except that the starting materials were replaced with 391-A, 391-B, 391-C and 391-D, everything else was the same as Example 2. LC MS: M/Z 706.32 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
Example 78
Synthesis of Compound 403
##STR00287##
[0240] Except that the starting materials were replaced with 403-A, 403-B, 403-C and 403-D, everything else was the same as Example 2. LC MS: M/Z 1118.44 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 79
Synthesis of Compound 417
##STR00288##
[0241] Except that the starting materials were replaced with 417-A, 417-B, 417-C and 417-D, everything else was the same as Example 2. LC MS: M/Z 817.33 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 80
Synthesis of Compound 428
##STR00289##
[0242] Except that the starting materials were replaced with 428-A, 428-B, 428-C and 428-D, everything else was the same as Example 2. LC MS: M/Z 737.29 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 81
Synthesis of Compound 415
##STR00290##
[0243] Except that the starting materials were replaced with 415-A, 415-B, 415-C and 415-D, everything else was the same as Example 2. LC MS: M/Z 695.25 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 82
Synthesis of Compound 231
##STR00291##
[0244] Except that the starting materials were replaced with 231-A, 231-B, 231-C and 231-D, everything else was the same as Example 2. LC MS: M/Z 766.34 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 83
Synthesis of Compound 4
##STR00292##
[0245] Except that the starting materials were replaced with 4-A, 4-B, 4-C and 4-D, everything else was the same as Example 2. LC MS: M/Z 841.33 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 84
Synthesis of Compound 30
##STR00293##
[0246] Except that the starting materials were replaced with 30-A, 30-B, 30-C and 30-D, everything else was the same as Example 2. LC MS: M/Z 706.33 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
Example 85
Synthesis of Compound 38
##STR00294##
[0247] Except that the starting materials were replaced with 38-A, 38-B, 38-C and 38-D, everything else was the same as Example 2. LC MS: M/Z 711.35 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
Example 86
Synthesis of Compound 43
##STR00295##
[0248] Except that the starting materials were replaced with 43-A, 43-B, 43-C and 43-D, everything else was the same as Example 2. LC MS: M/Z 968.39 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
Example 87
Synthesis of Compound 163
##STR00296##
[0249] Except that the starting materials were replaced with 163-A, 163-B, 163-C and 163-D, everything else was the same as Example 2. LC MS: M/Z 706.33 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
Example 88
Synthesis of Compound 478
##STR00297##
1) Synthesis of Intermediate 478-1
[0250] Under an argon atmosphere, 35.8 g (100 mmol) of compound 478-A, 18.3 g (100 mmol) of compound 478-B, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol %) of bis(dibenzylideneacetone)palladium, 953 mg (2 mmol %) of 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl and 1000 mL of xylene were added to a reaction container, and heated to 140 C. with stirring for 15 hours. The reaction mixture was cooled to room temperature, and 1000 ml of water was added thereto. The mixture was filtered. The filter cake was washed with a large amount of water and dried in vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 34.9 g of compound 478-1 with a HPLC purity of 99.5% and a yield of 82%. LC MS: M/Z 425.14 (M+).
[0251] .sup.1H NMR (400 MHz, DMSO-d6) 6.91 (m, 1H), 7.02 (s, 1H), 7.23 (m, 1H), 7.31 (m, 2H), 7.37-7.48 (m, 3H), 7.48-7.57 (m, 2H), 7.53-7.62 (m, 1H), 7.65-7.72 (m, 2H), 7.77 (t, 1H), 7.95-8.01 (m, 2H), 8.01-8.09 (m, 2H), 8.12 (m, 1H).
2) Synthesis of Intermediate 478-2
[0252] Under an argon atmosphere, 42.5 g (100 mmol) of compound 478-1, 27.3 g (100 mmol) of compound 478-C, 23.4 g (240 mmol) of sodium tert-butoxide, 575 mg (1 mmol %) of bis(dibenzylideneacetone)palladium, 953 mg (2 mmol %) of 2-dicyclohexylphosphine-2,4,6-triisopropylbiphenyl and 1000 mL of xylene were added to a reaction container, and heated to 140 C. with stirring for 15 hours. The reaction mixture was cooled to room temperature, and 1000 ml of water was added thereto. The mixture was filtered. The filter cake was washed with a large amount of water and dried in vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 51.3 g of compound 478-2 with a HPLC purity of 99.5% and a yield of 83%. LC MS: M/Z 617.24 (M+).
[0253] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 6.91 (m, 1H), 6.95-7.01 (m, 1H), 7.18 (m, 1H), 7.23 (m, 1H), 7.26-7.62 (m, 12H), 7.68 (m, 1H), 7.77 (t, 1H), 7.82-7.91 (m, 2H), 7.95-8.01 (m, 2H), 8.01-8.09 (m, 2H), 8.09-8.15 (m, 1H).
3) Synthesis of Compound 478
[0254] Under an argon atmosphere, 61.8 g (100 mmol) of compound 478-2, 16.2 g (100 mmol) of compound 478-D, 787 mg (1 mmol %) of XPhos Pd G3, 50 ml (300 mmol) of 1.5 M potassium phosphate and 1000 ml of tetrahydrofuran (THF) were added to a reaction container and stirred under reflux overnight. After cooling to room temperature, 800 ml of water was added thereto, and a large amount of solid precipitated. The solid was filtered, and the filter cake was washed with water three times and dried in vacuum. The crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 52.8 g of compound 478 with a yield of 72% and a HPLC purity of 99.9%. LC MS: M/Z 733.30 (M+).
[0255] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 2.07 (m, 2H), 2.77-2.99 (m, 4H), 6.91 (m, 1H), 6.95-7.01 (m, 1H), 7.20 (m, 2H), 7.26-7.63 (m, 14H), 7.68 (m, 1H), 7.77 (t, 1H), 7.81-7.91 (m, 3H), 7.93 (d, 1H), 7.95-8.01 (m, 2H), 8.03 (m, 1H).
Example 89
Synthesis of Compound 479
##STR00298##
[0256] Except that the starting materials were replaced with 479-A, 479-B, 479-C and 479-D, everything else was the same as Example 88. LC MS: M/Z 743.36 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0257] .sup.1H NMR (400 MHz, DMSO-d6) 1.40-1.55 (m, 2H), 1.69 (s, 6H), 1.69-1.81 (m, 2H), 2.37-2.45 (m, 2H), 2.65-2.75 (m, 2H), 6.67 (m, 1H), 7.17-7.79 (m, 23H), 7.80-7.94 (m, 3H), 7.99-8.07 (m, 1H), 8.27 (d, 1H), 8.37 (s, 1H), 8.73-8.81 (m, 1H).
Example 90
Synthesis of Compound 480
##STR00299##
[0258] Except that the starting materials were replaced with 480-A, 480-B, 480-C and 480-D, everything else was the same as Example 88. LC MS: M/Z 865.43 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0259] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (d, 12H), 1.70-1.85 (m, 5H), 1.82-1.91 (m, 1H), 2.78-2.88 (m, 4H), 6.73 (m, 2H), 6.91 (m, 1H), 7.06 (m, 2H), 7.20-7.27 (m, 1H), 7.30-7.38 (m, 4H), 7.34-7.43 (m, 2H), 7.43-7.53 (m, 4H), 7.50-7.58 (m, 4H), 7.65-7.79 (m, 8H), 7.79-7.87 (m, 3H), 7.91 (m, 1H), 8.00-8.06 (m, 1H).
Example 91
Synthesis of Compound 481
##STR00300##
[0260] Except that the starting materials were replaced with 481-A, 481-B, 481-B and 481-D, everything else was the same as Example 88. LC MS: M/Z 687.22 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0261] .sup.1H NMR (400 MHz, DMSO-d6) 3.23 (m, 2H), 4.53-4.69 (m, 2H), 6.00 (d, 1H), 6.93 (d, 1H), 7.20 (m, 2H), 7.30-7.66 (m, 17H), 7.69-7.80 (m, 3H), 7.77-7.89 (m, 4H), 7.98-8.06 (m, 1H).
Example 92
Synthesis of Compound 482
##STR00301##
[0262] Except that the starting materials were replaced with 482-A, 482-B, 482-C and 482-D, everything else was the same as Example 88. LC MS: M/Z 804.28 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%.
[0263] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 5.75 (d, 1H), 6.33 (s, 2H), 6.54 (d, 1H), 6.95-7.08 (m, 1H), 7.04-7.13 (m, 4H), 7.18 (m, 1H), 7.20-7.29 (m, 3H), 7.31-7.67 (m, 13H), 7.77 (t, 1H), 7.85-7.95 (m, 3H), 8.06 (d, 1H), 8.17-8.25 (m, 2H), 8.45 (m, 1H).
Example 93
Synthesis of Compound 483
##STR00302##
[0264] Except that the starting materials were replaced with 483-A, 483-B, 483-C and 483-D, everything else was the same as Example 88. LC MS: M/Z 831.26 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0265] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 4.29 (s, 2H), 7.14-7.27 (m, 5H), 7.27-7.58 (m, 18H), 7.66-7.80 (m, 7H), 7.84-7.94 (m, 2H), 7.94-8.02 (m, 1H), 8.37 (s, 1H).
Example 94
Synthesis of Compound 484
##STR00303##
[0266] Except that the starting materials were replaced with 484-A, 484-B, 484-C and 484-D, everything else was the same as Example 88. LC MS: M/Z 792.24 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0267] .sup.1H NMR (400 MHz, DMSO-d6) 1.96-2.10 (m, 2H), 2.78-2.88 (m, 2H), 4.22-4.30 (m, 2H), 7.18 (m, 1H), 7.30-7.69 (m, 22H), 7.69-7.80 (m, 3H), 7.87-7.95 (m, 1H), 8.01 (d, 1H), 8.30 (d, 1H), 8.45 (m, 1H).
Example 95
Synthesis of Compound 485
##STR00304##
[0268] Except that the starting materials were replaced with 485-A, 485-B, 485-C and 485-D, everything else was the same as Example 88. LC MS: M/Z 799.42 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0269] .sup.1H NMR (400 MHz, DMSO-d6) 1.22 (d, 12H), 1.48 (s, 4H), 1.69 (s, 6H), 6.67 (m, 1H), 7.18 (m, 1H), 7.19-7.27 (m, 2H), 7.30-7.80 (m, 20H), 7.80-7.94 (m, 3H), 7.99-8.07 (m, 1H), 8.27 (d, 1H), 8.37 (s, 1H), 8.73-8.81 (m, 1H).
Example 96
Synthesis of Compound 486
##STR00305##
[0270] Except that the starting materials were replaced with 486-A, 486-B, 486-C and 486-D, everything else was the same as Example 88. LC MS: M/Z 838.36 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0271] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 3.18 (m, 1H), 3.30 (m, 1H), 4.14 (t, 2H), 6.44 (m, 1H), 6.70 (m, 1H), 6.80 (m, 1H), 6.87 (t, 1H), 6.99-7.27 (m, 7H), 7.27-7.38 (m, 4H), 7.34-7.44 (m, 6H), 7.39-7.53 (m, 7H), 7.48-7.57 (m, 1H), 7.70 (dd, 1H), 7.74-7.95 (m, 6H).
Example 97
Synthesis of Compound 487
##STR00306##
[0272] Except that the starting materials were replaced with 487-A, 487-B, 487-C and 487-D, everything else was the same as Example 88. LC MS: M/Z 922.40 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0273] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 4.83 (s, 2H), 7.00-7.10 (m, 3H), 7.08-7.14 (m, 1H), 7.14 (m, 1H), 7.14-7.27 (m, 3H), 7.27-7.50 (m, 21H), 7.50-7.58 (m, 2H), 7.59-7.67 (m, 2H), 7.67-7.78 (m, 3H), 7.74-7.83 (m, 2H), 7.85-7.91 (m, 1H), 8.06 (d, 1H), 8.16-8.24 (m, 2H).
Example 98
Synthesis of Compound 488
##STR00307##
[0274] Except that the starting materials were replaced with 488-A, 488-B, 488-C and 488-D, everything else was the same as Example 88. LC MS: M/Z 784.38 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0275] .sup.1H NMR (400 MHz, DMSO-d6) 1.32 (s, 8H), 1.69 (s, 6H), 2.98 (m, 2H), 3.61 (t, 2H), 7.04 (m, 1H), 7.11 (t, 1H), 7.23-7.35 (m, 1H), 7.31-7.39 (m, 4H), 7.39-7.50 (m, 5H), 7.50-7.59 (m, 5H), 7.67-7.82 (m, 8H), 7.85-7.91 (m, 1H), 8.00 (m, 1H), 8.06 (d, 1H), 8.22-8.31 (m, 2H).
Example 99
Synthesis of Compound 489
##STR00308##
[0276] Except that the starting materials were replaced with 489-A, 489-B, 489-C and 489-D, everything else was the same as Example 88. LC MS: M/Z 842.42 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0277] .sup.1H NMR (400 MHz, DMSO-d6) 1.32 (s, 8H), 1.69 (s, 6H), 1.96 (m, 2H), 2.64-2.86 (m, 2H), 3.37 (m, 2H), 6.44 (m, 1H), 6.73-6.84 (m, 2H), 6.87 (t, 1H), 6.99-7.06 (m, 2H), 7.06-7.27 (m, 9H), 7.30-7.59 (m, 14H), 7.72-7.79 (m, 2H), 7.82 (d, 1H), 7.83-7.92 (m, 2H).
Example 100
Synthesis of Compound 490
##STR00309##
[0278] Except that the starting materials were replaced with 490-A, 490-B, 490-C and 490-D, everything else was the same as Example 88. LC MS: M/Z 736.35 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0279] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 1.63-1.83 (m, 3H), 2.78-2.88 (m, 2H), 4.14-4.22 (m, 2H), 6.68 (s, 2H), 7.00 (m, 1H), 7.04-7.12 (m, 3H), 7.14-7.50 (m, 12H), 7.50-7.59 (m, 5H), 7.77 (t, 1H), 7.82 (d, 1H), 7.84-7.91 (m, 2H), 8.24-8.32 (m, 4H).
Example 101
Synthesis of Compound 491
##STR00310##
[0280] Except that the starting materials were replaced with 491-A, 491-B, 491-C and 491-D, everything else was the same as Example 88. LC MS: M/Z 632.32 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0281] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 1.96 (m, 2H), 2.55-2.81 (m, 2H), 2.85 (s, 3H), 3.37 (m, 2H), 6.95-7.12 (m, 8H), 7.19-7.31 (m, 5H), 7.31-7.50 (m, 5H), 7.50-7.57 (m, 1H), 7.76 (s, 1H), 7.84-7.92 (m, 1H), 8.00 (m, 1H), 8.16-8.26 (m, 1H), 8.37 (s, 1H), 8.90-9.00 (m, 1H).
Example 102
Synthesis of Compound 492
##STR00311##
[0282] Except that the starting materials were replaced with 492-A, 492-B, 492-C and 492-D, everything else was the same as Example 88. LC MS: M/Z 791.42 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0283] .sup.1H NMR (400 MHz, DMSO-d6) 1.02 (s, 9H), 1.69 (s, 6H), 2.77-2.89 (m, 2H), 3.26 (m, 1H), 3.48 (m, 1H), 4.34 (m, 1H), 4.50 (m, 1H), 6.95-7.04 (m, 3H), 7.04-7.14 (m, 10H), 7.14-7.29 (m, 8H), 7.30-7.50 (m, 4H), 7.50-7.57 (m, 1H), 7.71-7.92 (m, 6H).
Example 103
Synthesis of Compound 493
##STR00312##
[0284] Except that the starting materials were replaced with 493-A, 493-B, 493-C and 493-D, everything else was the same as Example 88. LC MS: M/Z 797.33 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0285] .sup.1H NMR (400 MHz, DMSO-d6) 1.93-2.08 (m, 4H), 2.63-2.81 (m, 4H), 2.84 (m, 4H), 3.43-3.54 (m, 2H), 3.54-3.65 (m, 2H), 7.05-7.14 (m, 2H), 7.30-7.39 (m, 4H), 7.39-7.50 (m, 4H), 7.50-7.60 (m, 5H), 7.64-7.83 (m, 8H), 7.88 (m, 1H), 8.06 (d, 1H), 8.26 (m, 2H).
Example 104
Synthesis of Compound 494
##STR00313##
[0286] Except that the starting materials were replaced with 494-A, 494-B, 494-C and 494-D, everything else was the same as Example 88. LC MS: M/Z 911.45 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%.
[0287] .sup.1H NMR (400 MHz, DMSO-d6) 1.40-1.54 (m, 2H), 1.66-1.93 (m, 19H), 2.37-2.45 (m, 1H), 2.62-2.75 (m, 6H), 6.95-7.01 (m, 1H), 7.13-7.22 (m, 3H), 7.23 (m, 1H), 7.30-7.57 (m, 12H), 7.62-7.70 (m, 3H), 7.77 (m, 2H), 7.81-7.92 (m, 3H), 8.16-8.24 (m, 3H), 8.37 (s, 1H).
Example 105
Synthesis of Compound 495
##STR00314##
[0288] Except that the starting materials were replaced with 495-A, 495-B, 495-C and 495-D, everything else was the same as Example 88. LC MS: M/Z 895.39 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0289] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 3.29 (s, 4H), 7.02-7.11 (m, 3H), 7.11 (t, 1H), 7.14-7.27 (m, 3H), 7.29-7.50 (m, 16H), 7.50-7.59 (m, 3H), 7.67-7.82 (m, 8H), 7.85-7.93 (m, 2H), 8.06 (d, 1H), 8.22-8.31 (m, 2H).
Example 106
Synthesis of Compound 496
##STR00315##
[0290] Except that the starting materials were replaced with 496-A, 496-B, 496-C and 496-D, everything else was the same as Example 88. LC MS: M/Z 842.38 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0291] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 1.70 (m, 2H), 2.58-2.64 (m, 1H), 7.11 (t, 1H), 7.19 (m, 1H), 7.23-7.30 (m, 2H), 7.30-7.67 (m, 24H), 7.67-7.74 (m, 1H), 7.71-7.78 (m, 2H), 7.74-7.82 (m, 2H), 7.82-7.91 (m, 2H), 8.06 (d, 1H), 8.17-8.27 (m, 2H).
Example 107
Synthesis of Compound 497
##STR00316##
[0292] Except that the starting materials were replaced with 497-A, 497-B, 497-C and 497-D, everything else was the same as Example 88. LC MS: M/Z 801.37 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0293] .sup.1H NMR (400 MHz, DMSO-d6) 1.40 (s, 2H), 1.69 (s, 6H), 6.95-7.04 (m, 2H), 7.04-7.12 (m, 4H), 7.19-7.29 (m, 4H), 7.35 (m, 3H), 7.42-7.50 (m, 2H), 7.50-7.62 (m, 8H), 7.66 (m, 1H), 7.70-7.79 (m, 6H), 7.81-7.92 (m, 2H), 8.07 (m, 1H), 8.37 (s, 1H), 8.84 (d, 1H), 8.95 (m, 1H), 9.07 (d, 1H).
Example 108
Synthesis of Compound 498
##STR00317##
[0294] Except that the starting materials were replaced with 498-A, 498-B, 498-C and 498-D, everything else was the same as Example 88. LC MS: M/Z 835.36 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0295] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 12H), 6.91 (m, 1H), 6.94-7.01 (m, 2H), 7.26-7.41 (m, 9H), 7.41-7.61 (m, 12H), 7.68 (m, 1H), 7.71-7.79 (m, 3H), 7.82-7.92 (m, 3H), 7.94-8.01 (m, 1H), 8.03 (m, 1H), 8.37 (s, 1H).
Example 109
Synthesis of Compound 499
##STR00318##
[0296] Except that the starting materials were replaced with 499-A, 499-B, 499-C and 499-D, everything else was the same as Example 88. LC MS: M/Z 866.39 (M+). Total yield of synthesis: 50%; HPLC purity: 99.9%.
[0297] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 12H), 2.72 (m, 2H), 3.70 (t, 2H), 5.14 (s, 2H), 6.91 (m, 1H), 6.95-7.01 (m, 1H), 7.06 (m, 1H), 7.26-7.50 (m, 15H), 7.50-7.58 (m, 5H), 7.68 (m, 1H), 7.71-7.78 (m, 2H), 7.82-7.91 (m, 3H), 7.95-8.01 (m, 1H), 8.03 (m, 1H), 8.37 (s, 1H).
Example 110
Synthesis of Compound 500
##STR00319##
[0298] Except that the starting materials were replaced with 500-A, 500-B, 500-C and 500-D, everything else was the same as Example 88. LC MS: M/Z 835.36 (M+). Total yield of synthesis: 51%; HPLC purity: 99.9%.
[0299] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 12H), 5.12 (d, 2H), 6.91 (m, 1H), 6.95-7.01 (m, 1H), 7.18 (m, 1H), 7.23 (m, 1H), 7.26-7.50 (m, 9H), 7.50-7.60 (m, 5H), 7.65-7.73 (m, 2H), 7.71-7.80 (m, 4H), 7.82-7.91 (m, 4H), 7.94-8.01 (m, 2H), 8.03 (m, 1H), 8.37 (s, 1H).
Example 111
Synthesis of Compound 501
##STR00320##
[0300] Except that the starting materials were replaced with 501-A, 501-B, 501-C and 501-D, everything else was the same as Example 88. LC MS: M/Z 743.34 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0301] .sup.1H NMR (400 MHz, DMSO-d6) 1.69 (s, 6H), 1.80 (m, 2H), 4.00 (m, 2H), 7.00 (m, 1H), 7.04-7.12 (m, 2H), 7.14-7.29 (m, 5H), 7.35 (m, 2H), 7.37-7.50 (m, 2H), 7.50-7.80 (m, 12H), 7.81-7.94 (m, 4H), 8.00-8.06 (m, 1H), 8.27 (d, 1H), 8.37 (s, 1H), 8.74-8.80 (m, 1H).
Example 112
Synthesis of Compound 502
##STR00321##
[0302] Except that the starting materials were replaced with 502-A, 502-B, 502-C and 502-D, everything else was the same as Example 88. LC MS: M/Z 1014.42 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0303] .sup.1H NMR (400 MHz, DMSO-d6) 1.60 (m, 2H), 1.69 (s, 12H), 3.10 (m, 2H), 6.00 (d, 1H), 6.93 (d, 1H), 6.96-7.01 (m, 1H), 7.06 (m, 1H), 7.14-7.23 (m, 2H), 7.29-7.60 (m, 18H), 7.63-7.70 (m, 3H), 7.71-7.78 (m, 3H), 7.81 (m, 1H), 7.82-7.91 (m, 3H), 8.17-8.24 (m, 3H), 8.24 (m, 1H), 8.37 (s, 1H).
Example 113
Synthesis of Compound 504
##STR00322## ##STR00323##
[0304] Except that the starting materials were replaced with 504-A, 504-B, 504-C and 504-D, everything else was the same as Example 88. LC MS: M/Z 827.52 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0305] .sup.1H NMR (500 MHz, DMSO-d6) 8.01 (s, 1H), 7.72 (m, 1H), 7.69-7.61 (m, 4H), 7.61 (m, 1H), 7.58-7.50 (m, 4H), 7.49-7.27 (m, 11H), 7.27-7.18 (m, 4H), 7.21-7.14 (m, 2H), 6.92 (d, 1H), 1.74 (s, 4H), 1.28 (s, 12H).
Example 114
Synthesis of Compound 507
##STR00324##
[0306] Except that the starting materials were replaced with 507-A, 507-B, 507-C and 507-D, everything else was the same as Example 88. LC MS: M/Z 781.46 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0307] .sup.1H NMR (500 MHz, DMSO-d6) 8.01 (s, 1H), 7.69-7.63 (m, 5H), 7.61 (m, 1H), 7.58-7.51 (m, 6H), 7.49-7.27 (m, 8H), 7.24 (d, 1H), 7.21-7.14 (m, 6H), 1.74 (s, 3H), 1.74 (s, 4H), 1.28 (s, 12H).
Example 115
Synthesis of Compound 509
##STR00325##
[0308] Except that the starting materials were replaced with 509-A, 509-B, 509-C and 509-D, everything else was the same as Example 88. LC MS: M/Z 914.21 (M+). Total yield of synthesis: 46%; HPLC purity: 99.9%.
[0309] .sup.1H NMR (500 MHz, DMSO-d6) 8.04-7.98 (m, 2H), 7.94 (d, 1H), 7.66 (m, 3H), 7.58-7.51 (m, 6H), 7.51-7.32 (m, 10H), 7.32-7.14 (m, 11H), 7.14-7.07 (m, 5H), 6.87 (m, 1H), 1.74 (s, 4H), 1.28 (s, 12H).
Example 116
Synthesis of Compound 514
##STR00326##
[0310] Except that the starting materials were replaced with 514-A, 514-B, 514-C and 514-D, everything else was the same as Example 88. LC MS: M/Z 789.40 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0311] .sup.1H NMR (500 MHz, DMSO-d6) 8.03 (m, 1H), 7.98-7.91 (m, 2H), 7.69-7.63 (m, 2H), 7.63-7.57 (m, 2H), 7.57-7.51 (m, 5H), 7.51-7.38 (m, 6H), 7.41-7.29 (m, 4H), 7.24 (d, 1H), 7.21-7.14 (m, 4H), 7.11 (d, 1H), 6.87 (m, 1H), 1.74 (s, 4H), 1.59 (s, 6H), 1.28 (d, 12H).
Example 117
Synthesis of Compound 519
##STR00327## ##STR00328##
[0312] Except that the starting materials were replaced with 519-A, 519-B, 519-C and 519-D, everything else was the same as Example 88. LC MS: M/Z 987.44 (M+). Total yield of synthesis: 47%; HPLC purity: 99.9%.
[0313] .sup.1H NMR (500 MHz, DMSO-d6) 8.06-8.00 (m, 2H), 7.90 (d, 1H), 7.84 (m, 2H), 7.73 (d, 1H), 7.69-7.63 (m, 3H), 7.65-7.59 (m, 2H), 7.59-7.21 (m, 21H), 7.21-7.14 (m, 6H), 6.91 (m, 1H), 6.82 (m, 2H), 1.74 (s, 4H), 1.28 (s, 12H).
Example 118
Synthesis of Compound 521
##STR00329## ##STR00330##
[0314] Except that the starting materials were replaced with 521-A, 521-B, 521-C and 521-D, everything else was the same as Example 88. LC MS: M/Z 865.43 (M+). Total yield of synthesis: 45%; HPLC purity: 99.9%.
[0315] .sup.1H NMR (500 MHz, DMSO-d6) 8.06-8.00 (m, 2H), 7.90 (d, 1H), 7.84 (m, 2H), 7.73 (d, 1H), 7.69-7.63 (m, 3H), 7.65-7.59 (m, 2H), 7.59-7.21 (m, 22H), 7.21-7.14 (m, 6H), 6.91 (m, 1H), 6.82 (m, 2H), 1.74 (s, 4H), 1.28 (d, 12H).
Example 119
Synthesis of Compound 524
##STR00331## ##STR00332##
[0316] Except that the starting materials were replaced with 524-A, 524-B, 524-C and 524-D, everything else was the same as Example 88. LC MS: M/Z 927.44 (M+). Total yield of synthesis: 44%; HPLC purity: 99.9%.
[0317] .sup.1H NMR (500 MHz, DMSO-d6) 8.01 (m, 1H), 7.94 (d, 1H), 7.81 (d, 1H), 7.73 (m, 1H), 7.69-7.63 (m, 2H), 7.60-7.52 (m, 5H), 7.51-7.32 (m, 8H), 7.32-7.13 (m, 17H), 7.10 (m, 2H), 6.87 (m, 1H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 120
Synthesis of Compound 526
##STR00333## ##STR00334##
[0318] Except that the starting materials were replaced with 526-A, 526-B, 526-C and 526-D, everything else was the same as Example 88. LC MS: M/Z 987.44 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0319] .sup.1H NMR (500 MHz, DMSO-d6) 7.93 (d, 1H), 7.84 (m, 3H), 7.75-7.69 (m, 2H), 7.69-7.51 (m, 10H), 7.48-7.21 (m, 16H), 7.20-7.14 (m, 4H), 7.14-7.06 (m, 2H), 6.88 (m, 1H), 6.82 (m, 2H), 1.74 (s, 4H), 1.28 (d, 12H).
Example 121
Synthesis of Compound 527
##STR00335## ##STR00336##
[0320] Except that the starting materials were replaced with 527-A, 527-B, 527-C and 527-D, everything else was the same as Example 88. LC MS: M/Z 919.48 (M+). Total yield of synthesis: 48%; HPLC purity: 99.9%.
[0321] .sup.1H NMR (500 MHz, DMSO-d6) 8.06-8.01 (m, 1H), 7.89 (d, 1H), 7.80 (d, 1H), 7.75-7.66 (m, 4H), 7.65-7.27 (m, 16H), 7.25-7.14 (m, 6H), 7.09 (d, 1H), 6.96 (d, 1H), 1.60 (s, 12H), 1.31 (s, 12H), 0.93 (s, 6H).
Example 122
Synthesis of Compound 528
##STR00337## ##STR00338##
[0322] Except that the starting materials were replaced with 528-A, 528-B, 528-C and 528-D, everything else was the same as Example 88. LC MS: M/Z 885.48 (M+). Total yield of synthesis: 49%; HPLC purity: 99.9%.
[0323] .sup.1H NMR (500 MHz, DMSO-d6) 7.93 (d, 1H), 7.84 (d, 1H), 7.74 (m, 3H), 7.69-7.59 (m, 4H), 7.59-7.52 (m, 5H), 7.49 (m, 1H), 7.47-7.38 (m, 3H), 7.41-7.35 (m, 5H), 7.37-7.32 (m, 1H), 7.35-7.26 (m, 2H), 7.17 (m, 6H), 7.12 (d, 1H), 7.08 (d, 1H), 6.88 (m, 1H), 1.31 (s, 12H), 0.93 (s, 6H).
Device Example 1: Preparation of Red Light Emitting Device
##STR00339## ##STR00340## ##STR00341##
[0324] The preparation process is as follows: a transparent anode ITO film (thickness 150 nm) was formed on a glass substrate, to obtain a first electrode as an anode. Subsequently, a mixed material of compound T-1 and compound T-2 with a mixing ratio of 3:97 (mass ratio) was deposited on the surface of the anode by vacuum evaporation, to obtain a hole injection layer with a thickness of 10 nm. Then, compound T-2 was deposited, through evaporation, on the hole injection layer to obtain a first hole transport layer with a thickness of 100 nm. Subsequently, compound 1 of the present disclosure was deposited, through evaporation, on the first hole transport layer to obtain a second hole transport layer with a thickness of 10 nm. On the second hole transport layer, compound T-3 and compound T-4 were co-deposited, through evaporation, at a mass ratio of 95:5 to form an organic light-emitting layer with a thickness of 40 nm. Then, on the organic light-emitting layer, compound T-5 was deposited, through evaporation, to form a hole blocking layer (thickness 10 nm); thereafter, compound T-6 and LiQ at a mixing ratio of 4:6 (mass ratio) were deposited, through evaporation, to form an electron transport layer (thickness 30 nm). Finally, magnesium (Mg) and silver (Ag) were mixed at a deposition rate of 1:9, and deposited, through vacuum evaporation, on the electron injection layer as the second electrode 109. As such, the organic light-emitting device was manufactured.
Red-Light Device Examples 2-65
[0325] Except that compound 1 was replaced with compounds 20, 39, 305, 452, 457, 462, 467, 3, 28, 43, 127, 2, 11, 28, 134, 286, 6, 44, 293, 153, 172, 191, 210, 248, 267, 324, 400, 183, 204, 307, 160, 163, 170, 256, 145, 161, 175, 58, 77, 229, 57, 68, 115, 55, 64, 220, 96, 231, 100, 93, 98, 343, 381, 391, 449, 352, 363, 403, 417, 428, 419, 438, 355 and 415 respectively in forming the second hole transport layer, OLED devices were prepared by the same method as in Device Example 1.
Red-Light Device Control Examples 1-2
[0326] Except that compound 1 was replaced with compound HT-1 and compound HT-2 respectively in forming the second hole transport layer, OLED devices were prepared in the same manner as in Device Example 1.
[0327] For the OLED devices prepared above, the operating voltage and efficiency were calculated by a Keithley 2400 test system controlled by a computer. A Polaronix (McScience Co.) lifetime measurement system, which was equipped with a power supply and a photodiode as a detection unit, was used to obtain the device lifetime under dark conditions. Each group of Red-light Device Example and Red-light Device Control Example 1 were produced and tested in the same batch as the devices of Red-light Device Control Example 2. The operating voltage, efficiency and lifetime of the devices of Red-light Device Control Example 1 are all recorded as 1, and ratios of corresponding indicators of Device Examples 1-65 and Red-light Device Control Example 2 to Red-light Device Control Example 1 were respectively calculated, as shown in Table 1.
TABLE-US-00002 TABLE 1 Test results of Red-light Device Examples 1-65 and Device Control Examples 1-2 Type of Second hole Relative Relative Relative Example compound transport layer working voltage efficiency lifetime Red-light Device HT-1 1 1 1 Control Example 1 Red-light Device HT-2 1.071 1.03 1.427 Control Example 2 Red-light Device 1 compound 1 0.952 1.123 1.725 Example 1 Red-light Device 1 compound 20 0.945 1.115 1.81 Example 2 Red-light Device 1 compound 39 0.972 1.11 1.693 Example 3 Red-light Device 1 compound 305 0.949 1.099 1.657 Example 4 Red-light Device 1 compound 452 0.920 1.203 2.130 Example 5 Red-light Device 1 compound 457 0.931 1.215 1.957 Example 6 Red-light Device 1 compound 458 0.933 1.198 1.986 Example 7 Red-light Device 1 compound 462 0.954 1.186 2.105 Example 8 Red-light Device 1 compound 467 0.945 1.193 2.014 Example 9 Red-light Device 2 compound 3 0.931 1.164 1.785 Example 10 Red-light Device 2 compound 43 0.958 1.136 1.654 Example 11 Red-light Device 2 compound 127 0.946 1.147 1.765 Example 12 Red-light Device 3 compound 2 0.947 1.131 1.578 Example 13 Red-light Device 3 compound 11 0.957 1.127 1.589 Example 14 Red-light Device 3 compound 28 0.943 1.157 1.845 Example 15 Red-light Device 3 compound 134 0.934 1.095 1.585 Example 16 Red-light Device 3 compound 286 0.983 1.160 1.484 Example 17 Red-light Device 4 compound 6 0.976 1.174 1.457 Example 18 Red-light Device 4 compound 44 0.987 1.105 1.478 Example 19 Red-light Device 4 compound 293 0.976 1.135 1.567 Example 20 Red-light Device 5 compound 153 0.969 1.092 1.867 Example 21 Red-light Device 5 compound 172 0.968 1.159 1.681 Example 22 Red-light Device 5 compound 191 0.983 1.095 1.685 Example 23 Red-light Device 5 compound 210 0.972 1.16 1.545 Example 24 Red-light Device 5 compound 248 0.941 1.182 1.767 Example 25 Red-light Device 5 compound 267 0.978 1.183 1.945 Example 26 Red-light Device 5 compound 324 0.965 1.13 1.764 Example 27 Red-light Device 5 compound 400 0.974 1.135 1.943 Example 28 Red-light Device 6 compound 183 0.953 1.107 1.457 Example 29 Red-light Device 6 compound 204 0.947 1.098 1.543 Example 30 Red-light Device 6 compound 307 0.956 1.107 1.563 Example 31 Red-light Device 7 compound 160 0.987 1.134 1.587 Example 32 Red-light Device 7 compound 163 0.976 1.109 1.585 Example 33 Red-light Device 7 compound 170 0.965 1.107 1.456 Example 34 Red-light Device 7 compound 256 0.957 1.135 1.589 Example 35 Red-light Device 8 compound 145 0.977 1.132 1.564 Example 36 Red-light Device 8 compound 161 0.965 1.109 1.653 Example 37 Red-light Device 8 compound 175 0.975 1.127 1.589 Example 38 Red-light Device 9 compound 58 0.953 1.132 1.809 Example 39 Red-light Device 9 compound 77 0.933 1.101 1.960 Example 40 Red-light Device 9 compound 229 0.942 1.176 1.665 Example 41 Red-light Device 10 compound 57 0.976 1.156 1.535 Example 42 Red-light Device 11 compound 68 0.986 1.098 1.557 Example 43 Red-light Device 12 compound 115 0.965 1.156 1.883 Example 44 Red-light Device 13 compound 55 0.953 1.147 1.768 Example 45 Red-light Device 13 compound 64 0.945 1.153 1.457 Example 46 Red-light Device 13 compound 220 0.955 1.135 1.570 Example 47 Red-light Device 14 compound 96 0.932 1.105 1.872 Example 48 Red-light Device 14 compound 231 0.948 1.116 1.795 Example 49 Red-light Device 15 compound 100 0.956 1.079 1.457 Example 50 Red-light Device 15 compound 93 0.978 1.097 1.389 Example 51 Red-light Device 15 compound 98 0.969 1.105 1.401 Example 52 Red-light Device 16 compound 343 0.977 1.098 1.640 Example 53 Red-light Device 16 compound 381 0.956 1.156 1.567 Example 54 Red-light Device 16 compound 391 0.965 1.198 1.675 Example 55 Red-light Device 16 compound 449 0.969 1.125 1.594 Example 56 Red-light Device 17 compound 352 0.976 1.135 1.478 Example 57 Red-light Device 17 compound 363 0.958 1.104 1.558 Example 58 Red-light Device 17 compound 403 0.967 1.125 1.589 Example 59 Red-light Device 17 compound 417 0.976 1.146 1.654 Example 60 Red-light Device 18 compound 428 0.954 1.097 1.569 Example 61 Red-light Device 19 compound 419 0.968 1.173 1.694 Example 62 Red-light Device 19 compound 438 0.968 1.126 1.623 Example 63 Red-light Device 20 compound 355 0.968 1.126 1.596 Example 64 Red-light Device 20 compound 415 0.975 1.132 1.587 Example 65
[0328] According to the results in Table 1, when being used as the second hole transport layer of a red light-emitting device, the compounds used in Red-light Device Examples 1-65 enable respective formed devices to have lower voltages, higher luminous efficiencies (up to 20%), and significantly improved lifetime, compared with those formed from the compounds used in Red-light Device Control Examples 1-2. The possible reasons are as follows: compared with the compounds in the Control Examples, the introduction of a group on the side adjacent to the nitrogen atom can increase the triplet energy level of the compound; in addition, the introduced group may form a weak conjugation with the nitrogen atom, so that the material is more stable. Furthermore, from the aforementioned types of compounds, the efficiency and lifetime of devices made of these types of materials are greatly improved compared with the reference compounds, and there is not much difference between these types of materials in red light devices. Therefore, the compounds of the present disclosure are all suitable for red light devices.
Green-Light Device Example 1
##STR00342## ##STR00343## ##STR00344##
[0329] The preparation process is as follows: on a glass substrate, a transparent ITO film (thickness 150 nm) was formed by a magnetron sputtering process, to obtain a first electrode as an anode. A mixed material of compound T-1 and compound T-2 was deposited, through evaporation, on the surface of the anode as a hole injection layer. Then, T-2 (thickness 100 nm) and compound 1 of the present disclosure (thickness 40 nm) were deposited thereon to obtain a first hole transport layer and a second hole transport layer, respectively. Next, on the surface of the second hole transport layer, compound pGH, compound nGH and compound GD were co-deposited, through evaporation, at a mass ratio of 45:45:10 to form an organic light-emitting layer (thickness 40 nm). Subsequently, compound T-5 was deposited, through evaporation, on the surface of the organic light-emitting layer to form a hole blocking layer (10 nm thick); thereafter, compound T-6 and LiQ at a mixing ratio of 4:6 (mass ratio) were formed as an electron transport layer (30 nm thick). Finally, magnesium (Mg) and silver (Ag) were mixed and deposited at an evaporation rate of 1:9 on the surface of the electron transport layer, to form a second electrode with a thickness of 10 nm as a cathode. As such, the organic light-emitting device was manufactured.
Green-Light Device Examples 2-51
[0330] Except that compound 1 was replaced with compounds 4, 20, 30, 38, 452, 456, 457, 458, 461, 462, 464, 465, 467, 43, 127, 2, 11, 6, 293, 153, 191, 248, 400, 204, 307, 163, 256, 145, 175, 58, 77, 57, 68, 115, 55, 220, 96, 229, 100, 93, 98, 343, 391, 403,417, 428, 419, 438, 439 and 440 respectively in forming the second hole transport layer, OLED devices were prepared by the same method as in Green-light Device Example 1.
Green-Light Device Control Examples 1-4
[0331] Except that compound 1 was replaced with compounds HT-3, HT-4, HT-5 and HT-6 in forming the second hole transport layer, OLED devices were prepared by the same method as in Green-light Device Example 1.
##STR00345## ##STR00346##
TABLE-US-00003 TABLE 2 Test results of Green-light Device Examples 1-51 and Green-light Device Control Examples 1-4 Type of Second hole Relative Relative Relative Example compound transport layer working voltage efficiency lifetime Green-light Device HT-3 1 1 1 Control Example 1 Green-light Device HT-4 1.083 1.03 1.403 Control Example 2 Green-light Device HT-5 1.108 0.996 1.536 Control Example 3 Green-light Device HT-6 1.054 0.986 1.389 Control Example 4 Green-light Device 1 compound 1 0.955 1.126 1.870 Example 1 Green-light Device 1 compound 4 0.963 1.127 1.863 Example 2 Green-light Device 1 compound 20 0.967 1.132 1.869 Example 3 Green-light Device 1 compound 30 0.976 1.131 1.860 Example 4 Green-light Device 1 compound 38 0.942 1.145 1.972 Example 5 Green-light Device 1 compound 452 0.965 1.184 2.131 Example 6 Green-light Device 1 compound 456 0.943 1.161 1.985 Example 7 Green-light Device 1 compound 457 0.95 1.152 1.967 Example 8 Green-light Device 1 compound 458 0.957 1.156 1.981 Example 9 Green-light Device 1 compound 461 0.933 1.145 1.931 Example 10 Green-light Device 1 compound 462 0.975 1.159 1.956 Example 11 Green-light Device 1 compound 464 0.937 1.169 1.939 Example 12 Green-light Device 1 compound 465 0.941 1.171 1.917 Example 13 Green-light Device 1 compound 467 0.978 1.162 1.934 Example 14 Green-light Device 2 compound 43 1.043 1.067 1.561 Example 15 Green-light Device 2 compound 127 0.987 1.063 1.665 Example 16 Green-light Device 3 compound 2 0.998 1.100 1.602 Example 17 Green-light Device 3 compound 11 0.999 1.099 1.574 Example 18 Green-light Device 4 compound 6 0.987 1.080 1.583 Example 19 Green-light Device 4 compound 293 1.039 1.053 1.592 Example 20 Green-light Device 5 compound 153 0.981 1.074 1.553 Example 21 Green-light Device 5 compound 191 0.983 1.062 1.559 Example 22 Green-light Device 5 compound 248 1.050 1.050 1.641 Example 23 Green-light Device 5 compound 400 1.035 1.050 1.584 Example 24 Green-light Device 6 compound 204 1.048 1.097 1.662 Example 25 Green-light Device 6 compound 307 1.044 1.092 1.618 Example 26 Green-light Device 7 compound 163 0.996 1.094 1.693 Example 27 Green-light Device 7 compound 256 1.005 1.046 1.681 Example 28 Green-light Device 8 compound 145 0.997 1.071 1.543 Example 29 Green-light Device 8 compound 175 0.994 1.060 1.564 Example 30 Green-light Device 9 compound 58 1.002 1.040 1.638 Example 31 Green-light Device 9 compound 77 1.047 1.050 1.587 Example 32 Green-light Device 10 compound 57 1.014 1.083 1.663 Example 33 Green-light Device 11 compound 68 1.048 1.068 1.677 Example 34 Green-light Device 12 compound 115 1.039 1.077 1.665 Example 35 Green-light Device 13 compound 55 1.029 1.055 1.671 Example 36 Green-light Device 13 compound 220 1.014 1.051 1.577 Example 37 Green-light Device 14 compound 96 1.042 1.085 1.640 Example 38 Green-light Device 14 compound 231 1.044 1.083 1.556 Example 39 Green-light Device 15 compound 100 1.004 1.077 1.605 Example 40 Green-light Device 15 compound 93 1.046 1.059 1.555 Example 41 Green-light Device 15 compound 98 1.008 1.063 1.599 Example 42 Green-light Device 16 compound 343 1.041 1.043 1.669 Example 43 Green-light Device 16 compound 391 1.012 1.057 1.683 Example 44 Green-light Device 17 compound 403 1.008 1.095 1.598 Example 45 Green-light Device 17 compound 417 0.984 1.073 1.613 Example 46 Green-light Device 18 compound 428 1.017 1.041 1.543 Example 47 Green-light Device 19 compound 419 0.983 1.065 1.554 Example 48 Green-light Device 19 compound 438 1.037 1.048 1.545 Example 49 Green-light Device 20 compound 355 0.982 1.056 1.665 Example 50 Green-light Device 20 compound 415 1.030 1.082 1.549 Example 51
[0332] According to the results in Table 2, when being used as the second hole transport layer of a green light-emitting device, the compounds used in Green-light Device Examples 1 to 51 enable respective formed devices to have lower voltages, higher luminous efficiencies, and significantly improved lifetime, compared with those formed from compounds used in Green-light Device Control Examples 1 to 4. In addition, Green-light Device Examples 15 to 51 (with heteroatoms in A ring or B ring) have lower efficiency and shorter lifetime than those of Green-light Device Examples 1 to 14 (without heteroatoms in A ring or B ring). However, when the compounds in Examples 15 to 51 were used in red light devices, they had the same gain effect as the compounds without heteroatoms in A ring and B ring. The reason may be that, in green light devices, the energy of excitons is higher, which requires higher thermal and electrical stability of the materials. There are some unstable sites (such as some heteroatoms) in these compounds, which leads to a decrease in the efficiency and lifetime of the device. In addition, in Example 6, deuterium atoms were introduced into compound 452, which improved the lifetime of the device.
[0333] In summary, regardless of whether A ring or B ring of the compound of the present disclosure contains heteroatoms, when such compound is applied to a red light device, the voltage of the device is significantly reduced, and the efficiency and lifetime of the device are greatly improved. When A ring or B ring contains heteroatoms, such compound is not suitable for application in a green light device. When A ring or B ring does not contain heteroatoms, the voltage of the green light device is significantly reduced, and the efficiency and lifetime of the green light device are greatly improved, which is more suitable for application in green light devices.
Blue-Light Device Example 1: Preparation of OLED Device
##STR00347## ##STR00348## ##STR00349##
[0334] The preparation process is as follows:
[0335] 1) A transparent anode ITO film (thickness 150 nm) was formed on a glass substrate, to obtain a first electrode as an anode.
[0336] 2) Compound F4-TCNQ was deposited, through vacuum evaporation, on the surface of the anode, to form a hole injection layer with a thickness of 10 nm. Compound NPB (thickness 100 nm) and compound 1 (40 nm) were deposited, through vacuum evaporation, on the hole injection layer, to form a first hole transport layer and a second hole transport layer, respectively.
[0337] 4) On the surface of the second hole transport layer, an emission layer (EML) with a thickness of 10 nm was formed by taking compound BH-1 as a main component and doping BD-1 at a film thickness ratio of 100:3.
[0338] 5) ET-01 and LiQ were deposited, through evaporation, at a film thickness ratio of 1:1 on the EML, to form an electron transport layer (ETL) with a thickness of 30 nm, and Yb was deposited, through evaporation, on the electron transport layer to form an electron injection layer (EIL) with a thickness of 15 angstroms.
[0339] 6) Magnesium (Mg) and silver (Ag) were deposited, through vacuum evaporation, at a film thickness ratio of 1:9 on the electron injection layer, to form a cathode with a thickness of 11 nm.
[0340] 7) CP-1 with a thickness of 65 nm was deposited, through evaporation, on the cathode, to serve as an organic cover layer (CPL). As such, the organic light-emitting device was manufactured.
Blue-Light Device Examples 2-105
[0341] Except that compound 1 was replaced with compounds 4, 20, 30, 38, 39, 305, 457, 458, 462, 463, 464, 465, 466, 467, 479, 480, 485, 494, 504, 507, 509, 514, 519, 521, 524, 526, 527, 528, 3, 28, 43, 127, 2, 11, 134, 286, 478, 481, 493, 6, 44, 293, 153, 172, 191, 210, 248, 267, 324, 400, 486, 487, 488, 489, 491, 492, 495, 183, 204, 307, 160, 163, 170, 256, 145, 161, 175, 58, 77, 482, 490, 499, 57, 68, 115, 55, 64, 220, 484, 96, 229, 483, 100, 93, 98, 496, 497, 498, 500, 501, 502, 343, 381, 391, 449, 352, 363, 403, 417, 428, 419, 438, 355 and 439 respectively in forming the second hole transport layer, OLED devices were prepared by the same method as in Blue-light Device Example 1.
Blue-Light Device Control Examples 1-7
[0342] Except that compound 1 was replaced with compound HT-1, HT-2, HT-3, HT-4, HT-5, HT-6 and compound HT-7 respectively in forming the second hole transport layer, OLED devices were prepared by the same method as in Blue-light Device Example 1.
[0343] Each of the above Device Examples and Device Control Examples were produced and tested in the same batch as the devices of Device Control Example 1. The operating voltage, efficiency and lifetime of the device of Device Control Example 1 are all recorded as 1, and the ratios of corresponding indicators of Device Examples 1-105 and Device Control Examples 2-7 to Device Control Example 1 were respectively calculated, as shown in Table 3.
TABLE-US-00004 TABLE 3 Test results of Blue-light Device Examples 1-105 and Device Control Examples 1-7 Type of Second hole Relative Relative Relative Example compound transport layer working voltage efficiency lifetime Blue-light Device HT-1 1 1 1 Control Examples 1 Blue-light Device HT-2 1.135 0.976 0.90 Control Examples 2 Blue-light Device HT-3 0.986 1.035 1.210 Control Examples 3 Blue-light Device HT-4 1.036 1.010 0.965 Control Examples 4 Blue-light Device HT-5 1.231 0.976 1.015 Control Examples 5 Blue-light Device HT-6 1.136 1.113 1.214 Control Examples 6 Blue-light Device HT-7 1.158 1.096 1.104 Control Examples 7 Blue-light Device 1 compound 1 0.940 1.210 1.675 Example 1 Blue-light Device 1 compound 4 0.956 1.175 1.535 Example 2 Blue-light Device 1 compound 20 0.961 1.136 1.765 Example 3 Blue-light Device 1 compound 30 0.953 1.158 1.679 Example 4 Blue-light Device 1 compound 38 0.972 1.196 1.456 Example 5 Blue-light Device 1 compound 39 0.988 1.147 1.765 Example 6 Blue-light Device 1 compound 305 0.961 1.157 1.765 Example 7 Blue-light Device 1 compound 457 0.945 1.196 1.887 Example 8 Blue-light Device 1 compound 458 0.940 1.176 1.901 Example 9 Blue-light Device 1 compound 462 0.946 1.187 1.915 Example 10 Blue-light Device 1 compound 463 0.957 1.189 1.898 Example 11 Blue-light Device 1 compound 464 0.965 1.175 1.932 Example 12 Blue-light Device 1 compound 465 0.945 1.183 1.967 Example 13 Blue-light Device 1 compound 466 0.963 1.196 1.967 Example 14 Blue-light Device 1 compound 467 0.975 1.173 1.898 Example 15 Blue-light Device 1 compound 479 0.965 1.298 1.978 Example 16 Blue-light Device 1 compound 480 0.956 1.287 2.136 Example 17 Blue-light Device 1 compound 485 0.969 1.295 2.108 Example 18 Blue-light Device 1 compound 494 0.943 1.335 2.103 Example 19 Blue-light Device 1 compound 504 0.936 1.361 2.315 Example 20 Blue-light Device 1 compound 507 0.948 1.313 1.993 Example 21 Blue-light Device 1 compound 509 0.958 1.306 2.008 Example 22 Blue-light Device 1 compound 514 0.967 1.296 2.189 Example 23 Blue-light Device 1 compound 519 0.976 1.231 1.989 Example 24 Blue-light Device 1 compound 521 0.958 1.203 2.031 Example 25 Blue-light Device 1 compound 524 0.960 1.298 2.065 Example 26 Blue-light Device 1 compound 526 0.953 1.207 2.187 Example 27 Blue-light Device 1 compound 527 0.967 1.298 2.201 Example 28 Blue-light Device 1 compound 528 0.971 1.306 2.109 Example 29 Blue-light Device 2 compound 3 0.978 1.153 1.767 Example 30 Blue-light Device 2 compound 28 0.965 1.176 1.891 Example 31 Blue-light Device 2 compound 43 0.957 1.189 1.764 Example 32 Blue-light Device 2 compound 127 0.952 1.177 1.976 Example 33 Blue-light Device 3 compound 2 0.968 1.169 1.825 Example 34 Blue-light Device 3 compound 11 0.974 1.175 1.919 Example 35 Blue-light Device 3 compound 134 0.965 1.168 1.869 Example 36 Blue-light Device 3 compound 286 0.967 1.181 1.686 Example 37 Blue-light Device 3 compound 478 0.954 1.205 1.992 Example 38 Blue-light Device 3 compound 481 0.971 1.193 2.015 Example 39 Blue-light Device 3 compound 493 0.965 1.216 1.989 Example 40 Blue-light Device 4 compound 6 0.976 1.178 1.654 Example 41 Blue-light Device 4 compound 44 0.979 1.168 1.587 Example 42 Blue-light Device 4 compound 293 0.953 1.186 1.596 Example 43 Blue-light Device 5 compound 153 0.971 1.195 1.865 Example 44 Blue-light Device 5 compound 172 0.963 1.186 1.690 Example 45 Blue-light Device 5 compound 191 0.954 1.178 1.774 Example 46 Blue-light Device 5 compound 210 0.976 1.157 1.636 Example 47 Blue-light Device 5 compound 248 0.958 1.196 1.858 Example 48 Blue-light Device 5 compound 267 0.969 1.185 1.967 Example 49 Blue-light Device 5 compound 324 0.971 1.174 1.853 Example 50 Blue-light Device 5 compound 400 0.979 1.176 1.941 Example 51 Blue-light Device 5 compound 486 0.981 1.218 1.995 Example 52 Blue-light Device 5 compound 487 0.954 1.225 1.967 Example 53 Blue-light Device 5 compound 488 0.965 1.219 2.034 Example 54 Blue-light Device 5 compound 489 0.968 1.237 2.056 Example 55 Blue-light Device 5 compound 491 0.972 1.219 2.135 Example 56 Blue-light Device 5 compound 492 0.963 1.231 2.178 Example 57 Blue-light Device 5 compound 495 0.957 1.220 2.164 Example 58 Blue-light Device 6 compound 183 0.963 1.161 1.587 Example 59 Blue-light Device 6 compound 204 0.949 1.176 1.654 Example 60 Blue-light Device 6 compound 307 0.956 1.158 1.674 Example 61 Blue-light Device 7 compound 160 0.977 1.161 1.696 Example 62 Blue-light Device 7 compound 163 0.968 1.175 1.671 Example 63 Blue-light Device 7 compound 170 0.955 1.169 1.581 Example 64 Blue-light Device 7 compound 256 0.968 1.186 1.678 Example 65 Blue-light Device 8 compound 145 0.965 1.174 1.675 Example 66 Blue-light Device 8 compound 161 0.954 1.165 1.742 Example 67 Blue-light Device 8 compound 175 0.966 1.173 1.698 Example 68 Blue-light Device 9 compound 58 0.962 1.181 1.910 Example 69 Blue-light Device 9 compound 77 0.951 1.169 1.871 Example 70 Blue-light Device 9 compound 482 0.963 1.198 1.816 Example 71 Blue-light Device 9 compound 490 0.958 1.201 2.103 Example 72 Blue-light Device 9 compound 499 0.967 1.213 2.098 Example 73 Blue-light Device 10 compound 57 0.958 1.164 1.657 Example 74 Blue-light Device 11 compound 68 0.967 1.175 1.668 Example 75 Blue-light Device 12 compound 115 0.956 1.168 1.992 Example 76 Blue-light Device 13 compound 55 0.957 1.158 1.657 Example 77 Blue-light Device 13 compound 64 0.958 1.164 1.566 Example 78 Blue-light Device 13 compound 220 0.961 1.167 1.681 Example 79 Blue-light Device 13 compound 484 0.974 1.215 1.986 Example 80 Blue-light Device 14 compound 96 0.967 1.105 1.863 Example 81 Blue-light Device 14 compound 229 0.958 1.178 1.574 Example 82 Blue-light Device 14 compound 483 0.967 1.223 2.015 Example 83 Blue-light Device 15 compound 100 0.969 1.159 1.679 Example 84 Blue-light Device 16 compound 93 0.971 1.176 1.769 Example 85 Blue-light Device 16 compound 98 0.972 1.195 1.890 Example 86 Blue-light Device 16 compound 496 0.961 1.236 2.105 Example 87 Blue-light Device 16 compound 497 0.958 1.219 2.076 Example 88 Blue-light Device 16 compound 498 0.956 1.238 2.010 Example 89 Blue-light Device 16 compound 500 0.967 1.215 2.045 Example 90 Blue-light Device 16 compound 501 0.965 1.209 2.145 Example 91 Blue-light Device 16 compound 502 0.957 1.217 2.236 Example 92 Blue-light Device 17 compound 343 0.970 1.165 1.640 Example 93 Blue-light Device 17 compound 381 0.964 1.158 1.567 Example 94 Blue-light Device 17 compound 391 0.955 1.184 1.675 Example 95 Blue-light Device 17 compound 449 0.958 1.156 1.594 Example 96 Blue-light Device 18 compound 352 0.967 1.167 1.478 Example 97 Blue-light Device 18 compound 363 0.969 1.176 1.558 Example 98 Blue-light Device 18 compound 403 0.956 1.185 1.589 Example 99 Blue-light Device 18 compound 417 0.965 1.176 1.654 Example 100 Blue-light Device 19 compound 428 0.963 1.167 1.569 Example 101 Blue-light Device 20 compound 419 0.959 1.184 1.694 Example 102 Blue-light Device 20 compound 438 0.949 1.198 1.587 Example 103 Blue-light Device 21 compound 355 0.957 1.176 1.587 Example 104 Blue-light Device 21 compound 439 0.974 1.189 1.587 Example 105
[0344] According to the results in Table 3, when being used as the second hole transport layer of a blue light-emitting device, the compounds used in Blue-light Device Examples 1 to 105 enable respective formed devices to have lower voltages, higher luminous efficiencies, and significantly improved lifetime, compared with those formed from the compounds used in Blue-light Device Control Examples 1 to 7. Moreover, the efficiencies and lifetime of Blue-light Device Examples 16-29, Examples 38-40, Examples 52-58, Examples 71-73, Example 80, Example 83, and Examples 87-92 (introducing a benzene ring between the N atom and the matrix of an aromatic alkyl substituent) are greatly improved compared with other Examples. The possible reason is that, after the introduction of the benzene ring, the conjugation of the molecules is increased, and the degree of electron delocalization is increased, which leads to a decrease in the triplet energy level. As a result, in blue light devices, the efficiency and lifetime of the material can be greatly improved.
[0345] Therefore, the compounds of the present disclosure has great application value in organic optoelectronic devices.
[0346] The foregoing is only preferred specific implementations of the present disclosure, but the protection scope of the present disclosure is not limited thereto. Any skilled in the art can make equivalent replacements or variants according to the technical scheme and inventive concept of the present disclosure within the technical scope disclosed by the present disclosure, which should be covered by the protection scope of the present disclosure.