Compound, Organic Electroluminescent Device Containing Same and Application Thereof
20220158095 · 2022-05-19
Inventors
Cpc classification
C07D409/12
CHEMISTRY; METALLURGY
C07C211/61
CHEMISTRY; METALLURGY
C07C211/58
CHEMISTRY; METALLURGY
C07D405/12
CHEMISTRY; METALLURGY
H10K85/6574
ELECTRICITY
H10K85/626
ELECTRICITY
C07D209/86
CHEMISTRY; METALLURGY
H10K85/6572
ELECTRICITY
H10K85/633
ELECTRICITY
H10K85/636
ELECTRICITY
H10K85/6576
ELECTRICITY
International classification
C07C211/58
CHEMISTRY; METALLURGY
C07C211/61
CHEMISTRY; METALLURGY
C07D209/86
CHEMISTRY; METALLURGY
Abstract
A compound, an organic electroluminescent device containing the compound, and an application thereof. The compound has a structure shown in (I).
Claims
1. A compound having a structure as shown in Formula (I): ##STR00481## in the Formula (I), Ar.sup.1 and Ar.sup.2 are each independently selected from H, a substituted or unsubstituted C.sub.6-C.sub.50 aryl, a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl, a substituted or unsubstituted C.sub.6-C.sub.50 fused aryl, a substituted or unsubstituted C.sub.3-C.sub.30 fused heteroaryl; and when Ar.sup.1 is H, L.sup.1 is not a single bond; when Ar.sup.2 is H, L.sup.2 is not a single bond; Ar.sup.3 is selected from a substituted or unsubstituted C.sub.6-C.sub.50 aryl, a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl, a substituted or unsubstituted C.sub.6-C.sub.50 fused aryl, and a substituted or unsubstituted C.sub.3-C.sub.30 fused heteroaryl; L.sup.1-L.sup.3 are each independently selected from a single bond, a substituted or unsubstituted C.sub.1-C.sub.10 alkylene, a substituted or unsubstituted C.sub.6-C.sub.50 arylene, and a substituted or unsubstituted C.sub.3-C.sub.30 heteroarylene group; m is an integer of 0-6, and n is an integer of 0-15; R.sup.1 is each independently selected from H, a halogen, carbonyl, carboxyl, amino, amido, cyano, nitryl, an ester group, hydroxyl, silicyl, a substituted or unsubstituted C.sub.1-C.sub.20 alkyl, a substituted or unsubstituted C.sub.3-C.sub.20 cycloalkyl, a substituted or unsubstituted C.sub.2-C.sub.20 alkenyl, a substituted or unsubstituted C.sub.2-C.sub.20 alkynyl, a substituted or unsubstituted C.sub.1-C.sub.20 alkoxy, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkoxy, a substituted or unsubstituted C.sub.6-C.sub.50 aryl, a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl, and a C.sub.6-C.sub.50 fused aryl; R.sup.2 is, on each occurrence, a substituent of Ar.sup.1-Ar.sup.3, L.sup.1-L.sup.3, R.sup.1 or the naphthalene ring in the Formula (I), and is each independently selected from H, a halogen, carbonyl, carboxyl, amino, amido, cyano, nitryl, an ester group, hydroxyl, a C.sub.1-C.sub.10 silicyl, a substituted or unsubstituted C.sub.1-C.sub.20 alkyl, a substituted or unsubstituted C.sub.3-C.sub.20 cycloalkyl, a substituted or unsubstituted C.sub.2-C.sub.12 alkenyl, a substituted or unsubstituted C.sub.2-C.sub.12 alkynyl, a substituted or unsubstituted C.sub.1-C.sub.12 alkoxy, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkoxy, a substituted or unsubstituted C.sub.6-C.sub.50 aryl, a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl, and a C.sub.6-C.sub.50 fused aryl; the group ##STR00482## is located in an ortho position of the group ##STR00483## and neither R.sup.1 nor R.sup.2 is amido; or Ar.sup.1 is a substituted or unsubstituted C.sub.6-C.sub.30 aryl or a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl, Ar.sup.2 is a substituted or unsubstituted benzodimethyl fluorenyl, and Ar.sup.3 is a substituted or unsubstituted naphthyl; when each substituted or unsubstituted group has a substituent, the substituent is selected from one or more of a halogen, cyano, nitryl, an ester group, hydroxyl, carbonyl, carboxyl, cyano, amido, a C.sub.1-C.sub.10 silicyl, a C.sub.1-C.sub.20 alkyl, a C.sub.3-C.sub.20 cycloalkyl, a C.sub.2-C.sub.20 alkenyl, a C.sub.2-C.sub.10 alkynyl, a C.sub.1-C.sub.20 alkoxy or thioalkoxy, a C.sub.6-C.sub.30 arylamino, a C.sub.3-C.sub.30 heteroarylamino, a C.sub.6-C.sub.30 monocyclic or fused-cyclic aryl, a C.sub.3-C.sub.30 monocyclic or fused-cyclic heteroaryl.
2. The compound according to claim 1, wherein the group ##STR00484## is located in an ortho position of the group ##STR00485## Ar.sup.1-Ar.sup.3 are each independently selected from a substituted or unsubstituted C.sub.6-C.sub.30 aryl or a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl, L.sup.1-L.sup.3 are each independently selected from a single bond, a substituted or unsubstituted C.sub.6-C.sub.30 alkylene, and a substituted or unsubstituted C.sub.6-C.sub.30 heteroarylene group; m is an integer of 1-6, and n is an integer of 1-15; R.sup.1 is each independently selected from one of H, a halogen, cyano, nitryl, hydroxyl, silicyl, a C.sub.1-C.sub.20 chain-typed alkyl, a C.sub.3-C.sub.20 cycloalkyl, a C.sub.2-C.sub.20 alkenyl, a C.sub.2-C.sub.20 alkynyl, a C.sub.1-C.sub.20 alkoxy, a substituted or unsubstituted C.sub.6-C.sub.30 aryl, and a substituted or unsubstituted C.sub.1-C.sub.30 heteroaryl; R.sup.2 is, on each occurrence, a substituent of Ar.sup.1-Ar.sup.3, L.sup.1-L.sup.3, R.sup.1 or the naphthalene ring in the Formula (I), and is each independently selected from one of H, a substituted or unsubstituted C.sub.3-C.sub.30 cycloalkyl; and at least one R.sup.2 is selected from one of the substituted or unsubstituted C.sub.3-C.sub.30 cycloalkyl; when each substituted or unsubstituted group has a substituent, the substituent is selected from one or a combination of more of a halogen, a C.sub.1-C.sub.20 chain-typed alkyl, a C.sub.3-C.sub.20 cycloalkyl, a C.sub.2-C.sub.20 alkenyl, a C.sub.1-C.sub.20 alkoxy or thioalkoxy, a C.sub.6-C.sub.30 monocyclic or fused-cyclic aryl, a C.sub.3-C.sub.30 monocyclic or fused-cyclic heteroaryl.
3. The compound according to claim 2, wherein L.sup.1 and L.sup.2 are each independently selected from a single bond, phenylene or naphthylene, and L.sup.3 is a single bond; Ar.sup.1 is a substituted or unsubstituted C.sub.10-C.sub.30 fused-cyclic aryl or a substituted or unsubstituted C.sub.6-C.sub.30 fused-cyclic heteroaryl; Ar.sup.2 is a substituted or unsubstituted C.sub.6-C.sub.30 monocyclic aryl or a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl; Ar.sup.3 is a substituted or unsubstituted naphthyl, a substituted or unsubstituted fluorenyl, or a substituted or unsubstituted dibenzo-X hetercyclopentadiene, X is O, N, S, or Si; when each substituted or unsubstituted group has a substituent, the substituent is selected from a C.sub.1-C.sub.20 chain-typed alkyl, a C.sub.3-C.sub.20 cycloalkyl, a C.sub.6-C.sub.30 aryl or a C.sub.3-C.sub.30 cycloalkyl; R.sup.2 is selected from one of the following structures: ##STR00486## ##STR00487## ##STR00488## preferably, Ar.sup.1 is selected from one of the following structures: ##STR00489## Ar.sup.2 is selected from one of the following structures: ##STR00490## wherein, the dotted line denotes an access site of a group; the representing method of lining across the benzene ring with the dotted line denotes that a linking site of a group may be in any bondable position on the benzene ring; preferably, the group ##STR00491## is located in a 1-position or 2-position on the naphthalene ring, and when the group ##STR00492## is located in the 1-position on the naphthalene ring, the group ##STR00493## is located in the 2-position on the naphthalene ring; preferably, R.sup.2 is each independently selected from cyclopentyl, cyclohexyl and cycloheptyl; more preferably, at least one of Ar.sup.1 and Ar.sup.2 has a substituent of substituted or unsubstituted C.sub.3-C.sub.20 cycloalkyl; further preferably, Ar.sup.2 has the substituent of substituted or unsubstituted C.sub.3-C.sub.20 cycloalkyl.
4. The compound according to claim 2, wherein the compound has a structure as shown in P1-P291: ##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## ##STR00573## ##STR00574## ##STR00575## ##STR00576## ##STR00577## ##STR00578## ##STR00579## ##STR00580## ##STR00581## ##STR00582## ##STR00583## ##STR00584## ##STR00585## ##STR00586## ##STR00587## ##STR00588## ##STR00589## ##STR00590## ##STR00591## ##STR00592## ##STR00593## ##STR00594##
5. The compound according to claim 1, wherein the compound has a structure as shown in Formula (II): ##STR00595## wherein, L.sup.1 and L.sup.2 are each independently selected from a single bond, a substituted or unsubstituted C.sub.6-C.sub.50 alkylene, a substituted or unsubstituted C.sub.3-C.sub.30 heteroarylene group; Ar.sup.1 and Ar.sup.2 are each independently selected from H, a substituted or unsubstituted C.sub.6-C.sub.50 aryl, a substituted or unsubstituted C.sub.6-C.sub.50 fused aryl, a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl, a substituted or unsubstituted C.sub.3-C.sub.30 fused heteroaryl; and when Ar.sup.1 is H, L.sup.1 is not a single bond, and when Ar.sup.2 is H, L.sup.2 is not a single bond; R.sup.1 and R.sup.2 are each independently selected from H, a halogen, carbonyl, carboxyl, cyano, amido, a C.sub.1-C.sub.20 alkyl, a C.sub.3-C.sub.20 cycloalkyl, a C.sub.2-C.sub.12 alkenyl, a C.sub.2-C.sub.12 alkynyl, a C.sub.1-C.sub.12 alkoxy, a substituted or unsubstituted C.sub.6-C.sub.50 aryl, a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl, a C.sub.6-C.sub.50 fused aryl; and R.sup.1 and R.sup.2 are linked on the naphthalene ring in a single bond way; m is an integer of 0-6, and n is an integer of 0-7; when the above-mentioned groups have a substituent, the substituent is each independently selected from one or more of a halogen, carbonyl, carboxyl, cyano, amido, a C.sub.1-C.sub.10 alkyl, a C.sub.3-C.sub.10 cycloalkyl, a C.sub.2-C.sub.10 alkenyl, a C.sub.1-C.sub.6 alkoxy, a C.sub.1-C.sub.6 thioalkoxy, a C.sub.6-C.sub.30 monocyclic or fused-cyclic aryl, a C.sub.3-C.sub.30 monocyclic or fused-cyclic heteroaryl.
6. The compound according to claim 5, wherein L.sup.1 and L.sup.2 are a single bond; R.sup.1 and R.sup.2 are H; Ar.sup.1 and Ar.sup.2 are each independently selected from a C.sub.6-C.sub.50 aryl or fused aryl, a C.sub.3-C.sub.30 heteroaryl or fused heteroaryl; preferably, Ar.sup.1 and Ar.sup.2 are each independently selected from the group consisting of substituted or unsubstituted: ##STR00596## ##STR00597## ##STR00598## ##STR00599## wherein, represents an access position of a group; more preferably, Ar.sup.1 and Ar.sup.2 are each independently selected from the group consisting of substituted or unsubstituted: ##STR00600## ##STR00601##
7. The compound according to claim 4, wherein the compound has a structure as shown in N1-N419: ##STR00602## ##STR00603## ##STR00604## ##STR00605## ##STR00606## ##STR00607## ##STR00608## ##STR00609## ##STR00610## ##STR00611## ##STR00612## ##STR00613## ##STR00614## ##STR00615## ##STR00616## ##STR00617## ##STR00618## ##STR00619## ##STR00620## ##STR00621## ##STR00622## ##STR00623## ##STR00624## ##STR00625## ##STR00626## ##STR00627## ##STR00628## ##STR00629## ##STR00630## ##STR00631## ##STR00632## ##STR00633## ##STR00634## ##STR00635## ##STR00636## ##STR00637## ##STR00638## ##STR00639## ##STR00640## ##STR00641## ##STR00642## ##STR00643## ##STR00644## ##STR00645## ##STR00646## ##STR00647## ##STR00648## ##STR00649## ##STR00650## ##STR00651## ##STR00652## ##STR00653## ##STR00654## ##STR00655## ##STR00656## ##STR00657## ##STR00658## ##STR00659## ##STR00660## ##STR00661## ##STR00662## ##STR00663## ##STR00664## ##STR00665## ##STR00666## ##STR00667## ##STR00668## ##STR00669## ##STR00670## ##STR00671## ##STR00672## ##STR00673## ##STR00674## ##STR00675## ##STR00676## ##STR00677## ##STR00678## ##STR00679## ##STR00680## ##STR00681## ##STR00682## ##STR00683## ##STR00684## ##STR00685## ##STR00686## ##STR00687## ##STR00688## ##STR00689## ##STR00690## ##STR00691## ##STR00692## ##STR00693## ##STR00694## ##STR00695##
8. The compound according to claim 1, wherein the compound has a structure as shown in Formula (III): ##STR00696## wherein Formula (B) is fused to Formula (A) along any one of the dotted line of a, b or c; L.sup.1 is selected from one of a single bond, a substituted or non-substituted C.sub.1-C.sub.10 alkylene, a substituted or non-substituted C.sub.6-C.sub.30 arylene, a substituted or non-substituted C.sub.3-C.sub.30 heteroarylene group; Ar.sup.1 is selected from one of a substituted or unsubstituted C.sub.6-C.sub.30 aryl, a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl; R.sup.1, R.sup.2, R.sup.3, R.sup.4 and R.sup.5 are each independently selected from halogen, amino, cyano, nitryl, an ester group, hydroxyl, a C.sub.1-C.sub.10 silicyl, a substituted or unsubstituted C.sub.1-C.sub.10 chain-typed alkyl, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkyl, a substituted or unsubstituted C.sub.2-C.sub.10 alkenyl, a substituted or unsubstituted C.sub.2-C.sub.10 alkynyl, a substituted or unsubstituted C.sub.1-C.sub.10 chain-typed alkoxy, a substituted or unsubstituted C.sub.3-C.sub.10 cycloalkoxy, a substituted or unsubstituted C.sub.6-C.sub.30 arylamino, a substituted or unsubstituted C.sub.3-C.sub.30 heteroarylamino, a substituted or unsubstituted C.sub.6-C.sub.30 aryl, a substituted or unsubstituted C.sub.3-C.sub.30 heteroaryl; m is an integer of 0-6, and when m≥2, R.sup.1 is same or different; n is an integer of 0-7, and when n≥2, R.sup.2 is same or different; p is an integer of 0-2, and when p=2, R.sup.3 is same or different; q is an integer of 0-3, and when q≥2, R.sup.4 is same or different; s is an integer of 0-4, and when s≥2, R.sup.5 is same or different; when the above-mentioned groups have a substituent, the substituent is selected from one or a combination of at least two of halogen, cyano, a C.sub.1-C.sub.10 chain-typed alkyl, a C.sub.3-C.sub.10 cycloalkyl, a C.sub.1-C.sub.6 alkoxy, a C.sub.1-C.sub.6 thioalkoxy, a C.sub.6-C.sub.30 arylamino, a C.sub.3-C.sub.30 heteroarylamino, a C.sub.6-C.sub.30 monocyclic aryl, a C.sub.10-C.sub.30 fused-cyclic aryl, a C.sub.3-C.sub.30 monocyclic heteroaryl, and a C.sub.6-C.sub.30 fused-cyclic heteroaryl.
9. The compound according to claim 8, wherein the compound has a structure as shown in the following Formula (3-1): ##STR00697## wherein Formula (B) is fused to Formula (A) along any one of the dotted line of a, b or c; preferably, wherein the compound has a structure as shown in the following Formula (3-2): ##STR00698## wherein Formula (B) is fused to Formula (A) along any one of the dotted line of a, b or c; preferably, in Formula (3-2), wherein s, p, n, m and q are 0.
10. (canceled)
11. (canceled)
12. The compound according to claim 9, wherein fluorenyl and the benzene ring are fused in the b position; preferably, wherein the L.sup.1 is selected from a single bond, or a substituted or unsubstituted phenylene, preferably, a single bond; the Ar.sup.1 is selected from one of a substituted or unsubstituted phenyl, a substituted or unsubstituted naphthyl, a substituted or unsubstituted phenanthryl, a substituted or unsubstituted dibenzofuryl, a substituted or unsubstituted dibenzothienyl, and a substituted or unsubstituted carbazolyl; the -L.sup.1-Ar.sup.1 is selected from one of phenyl, biphenyl, terphenyl, dibenzofuran, dibenzothiophene, carbazolyl or phenanthryl; when the above-mentioned groups have a substituent, the substituent is selected from one or a combination of at least two of a halogen, cyano, a C.sub.1-C.sub.10 chain-typed alkyl, a C.sub.3-C.sub.10 cycloalkyl, a C.sub.1-C.sub.6 alkoxy, a C.sub.1-C.sub.6 thioalkoxy, a C.sub.6-C.sub.30 arylamino, a C.sub.3-C.sub.30 heteroarylamino, a C.sub.6-C.sub.30 monocyclic aryl, a C.sub.10-C.sub.30 fused-cyclic aryl, a C.sub.3-C.sub.30 monocyclic heteroaryl, and a C.sub.6-C.sub.30 fused-cyclic heteroaryl.
13. (canceled)
14. The compound according to claim 8, wherein the compound has a structure as shown in T1-T255: ##STR00699## ##STR00700## ##STR00701## ##STR00702## ##STR00703## ##STR00704## ##STR00705## ##STR00706## ##STR00707## ##STR00708## ##STR00709## ##STR00710## ##STR00711## ##STR00712## ##STR00713## ##STR00714## ##STR00715## ##STR00716## ##STR00717## ##STR00718## ##STR00719## ##STR00720## ##STR00721## ##STR00722## ##STR00723## ##STR00724## ##STR00725## ##STR00726## ##STR00727## ##STR00728## ##STR00729## ##STR00730## ##STR00731## ##STR00732## ##STR00733## ##STR00734## ##STR00735## ##STR00736## ##STR00737## ##STR00738## ##STR00739## ##STR00740## ##STR00741## ##STR00742## ##STR00743## ##STR00744## ##STR00745## ##STR00746## ##STR00747## ##STR00748## ##STR00749## ##STR00750## ##STR00751## ##STR00752## ##STR00753## ##STR00754## ##STR00755## ##STR00756## ##STR00757## ##STR00758## ##STR00759## ##STR00760## ##STR00761## ##STR00762## ##STR00763## ##STR00764## ##STR00765## ##STR00766##
15. An application of the compound of claim 1 in an organic electroluminescent device, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner, electronic paper or an organic EL panel, and preferably as a hole-transport material or an electron blocking material.
16. An organic electroluminescent device, comprising a substrate, a first electrode, a second electrode, and at least one organic layer located between the first electrode and the second electrode, wherein the organic layer comprises at least one compound of claim 1.
17. The organic electroluminescent device according to claim 16, wherein the organic layer comprises a hole transport region, and the hole transport region comprises the compound of claim 1; preferably, the hole transport region comprises a hole transport layer and/or an electron blocking layer, wherein at least one of the hole transport layer and the electron blocking layer comprises the compound of claim 1.
18. An application of the compound of claim 6 in an organic electroluminescent device, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner, electronic paper or an organic EL panel, and preferably as a hole-transport material or an electron blocking material.
19. An application of the compound of claim 9 in an organic electroluminescent device, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information label, an electronic artificial skin sheet, a sheet-type scanner, electronic paper or an organic EL panel, and preferably as a hole-transport material or an electron blocking material.
20. An organic electroluminescent device, comprising a substrate, a first electrode, a second electrode, and at least one organic layer located between the first electrode and the second electrode, wherein the organic layer comprises at least one compound of claim 6.
21. An organic electroluminescent device, comprising a substrate, a first electrode, a second electrode, and at least one organic layer located between the first electrode and the second electrode, wherein the organic layer comprises at least one compound of claim 9.
22. The organic electroluminescent device according to claim 6, wherein the organic layer comprises a hole transport region, and the hole transport region comprises the compound of claim 6; preferably, the hole transport region comprises a hole transport layer and/or an electron blocking layer, wherein at least one of the hole transport layer and the electron blocking layer comprises the compound of claim 6.
23. The organic electroluminescent device according to claim 9, wherein the organic layer comprises a hole transport region, and the hole transport region comprises the compound of claim 9; preferably, the hole transport region comprises a hole transport layer and/or an electron blocking layer, wherein at least one of the hole transport layer and the electron blocking layer comprises the compound of claim 9.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0123]
[0124]
[0125]
[0126]
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0127] The technical solution of the present invention will be further described by reference to the following detailed embodiments. A person skilled in the art should know that the embodiments are merely used to help understanding the present invention but are not construed as limiting the scope of the invention.
Composition of the Organic Electroluminescent of the Present Invention
[0128] In a detailed embodiment, a substrate may be used below a first electrode or above a second electrode. The substrate is made of a glass or polymer material with excellent mechanical strength, heat stability, waterproofness and transparency. Moreover, the substrate as a display may be also provided with a thin film transistor (TFT).
[0129] The first electrode may be formed by a way of sputtering or depositing a material to be used as the first electrode on the substrate. The first electrode may be made of indium tin oxide (ITO), indium zinc oxide (IZO), SnO.sub.2, ZnO and other oxides, namely, transparent conductive materials and any combination thereof when the first electrode serves as an anode. The first electrode may be made of Mg, Ag, Al, Al—Li, Ca, Mg—In, Mg—Ag, and other metals or alloys and any combination thereof when the first electrode serves as a cathode.
[0130] The organic layer may be formed onto the electrodes by vacuum thermal evaporation, rotary coating, printing and other methods. The compound used as the organic layer may be organic small organic molecules, organic macromolecules and polymers, and combinations thereof.
[0131] The hole transport region is located between the anode and the luminescent layer. The hole transport region may be a hole transport layer (HTL) with a single-layer structure, including a single-layer HTL only containing a compound and a single-layer HTL containing a plurality of compounds. The hole transport region also may be a multilayered structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL) and an electron blocking layer (EBL).
[0132] In one aspect of the present invention, the electron blocking layer in the hole transport region may be selected from one or more of compounds of the present invention. At this time, HTL in the hole transport region may be selected from, but not limited to, phthalocyanine derivatives, e.g., CuPc, conductive polymers or polymers containing conductive dopants, such as, polyhenylene vinylene, polyaniline/dodecylbenzene sulfonic acid (Pam/DBSA), poly(3,4-ethylenedioxothiophene)/poly(4-styrene sulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly(4-styrene sulfonate) (Pani/PSS), aromatic amine derivatives, such as, compounds as shown in the following HT-1 to HT-34, or any combination thereof.
[0133] In another aspect of the present invention, the HTL in the hole transport region may be selected from one or more of compounds of the present invention. At this time, the electron blocking layer in the hole transport region may be selected from, but not limited to, phthalocyanine derivatives, e.g., CuPc, conductive polymers or polymers containing conductive dopants, such as, polyhenylene vinylene, polyaniline/dodecylbenzene sulfonic acid (Pam/DBSA), poly(3,4-ethylenedioxothiopheneypoly(4-styrene sulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly(4-styrene sulfonate) (Pani/PSS), aromatic amine derivatives, such as, compounds as shown in the following HT-1 to HT-34, or any combination thereof.
##STR00315## ##STR00316## ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## ##STR00322## ##STR00323## ##STR00324##
[0134] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer may be made of a single compound, or a combination of a plurality of compounds. For example, the hole injection layer may be one or more compounds as shown in the above HT-1 to HT-34, or one or more compounds as shown in the following HI-1 to HI-3, or one or more compounds as shown in the above HT-1 to HT-34 doped with one or more compounds as shown in the following HI-1 to HI-3.
##STR00325##
[0135] The luminescent layer includes a luminescent dye (namely, a dopant) which may emit different wavelength spectrum, and may further include a host material (Host) at the same time. The luminescent layer may be a single-color luminescent layer emitting red, green, blue and other single-color light. Multiple different colors of single-color luminescent layers may be arranged planarly according to pixel graphics and may be also piled together to form a colorful luminescent layer. Different colors of luminescent layers may be separated mutually or collected when piled together. The luminescent layer may be a single colorful luminescent layer emitting red, green, blue and other different colors of light.
[0136] According to different technologies, the luminescent layer may be made of fluorescent electroluminescent materials, phosphorescent electroluminescent materials. TADF luminescent materials and the like. A single luminescent technology or a combination of multiple different luminescent technologies may be used in an OLED device. These different luminescent materials classified by technologies may emit the same color of light, and also may emit different colors of light.
[0137] In one aspect of the present invention, the fluorescent electroluminescent technology is used in the luminescent layer. The fluorescent host material of the luminescent layer may be selected from, but not limited to one or more combinations listed in BFH-1 to BFH-17.
##STR00326## ##STR00327## ##STR00328## ##STR00329##
[0138] In one aspect of the present invention, the fluorescent electroluminescent technology is used in the luminescent layer. The fluorescent dopant of the luminescent layer may be selected from, but not limited to one or more combinations listed in BFD-1 to BFD-12.
##STR00330## ##STR00331## ##STR00332##
[0139] In one aspect of the present invention, the phosphorescent electroluminescent technology is used in the luminescent layer. The fluorescent host material of the luminescent layer may be selected from, but not limited to one or more compounds listed in GPH-1 to GPH-80.
##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346## ##STR00347## ##STR00348## ##STR00349## ##STR00350## ##STR00351## ##STR00352## ##STR00353##
[0140] In one aspect of the present invention, the phosphorescent electroluminescent technology is used in the luminescent layer. The fluorescent dopant of the luminescent layer may be selected from, but not limited to one or more combinations listed in GPD-1 to GPD-47.
##STR00354## ##STR00355## ##STR00356## ##STR00357## ##STR00358## ##STR00359## ##STR00360## ##STR00361## ##STR00362## ##STR00363##
[0141] where, D is deuterium.
[0142] In one aspect of the present invention, the phosphorescent electroluminescent technology is used in the luminescent layer. The fluorescent dopant of the luminescent layer may be selected from, but not limited to one or more combinations listed in RPD-1 to RPD-28.
##STR00364## ##STR00365## ##STR00366## ##STR00367## ##STR00368## ##STR00369## ##STR00370##
[0143] In one aspect of the preset invention, the phosphorescent electroluminescent technology is used in the luminescent layer. The fluorescent dopant of the luminescent layer may be selected from, but not limited to one or more combinations listed in YPD-1 to YPD-11.
##STR00371## ##STR00372## ##STR00373##
[0144] In one aspect of the present invention, the TADF luminescent technology is used in the luminescent layer. The fluorescent dopant of the luminescent layer may be selected from, but not limited to one or more combinations listed in TDE-1 to TDE-39.
##STR00374## ##STR00375## ##STR00376## ##STR00377## ##STR00378## ##STR00379## ##STR00380## ##STR00381##
[0145] In one aspect of the present invention, the TADF luminescent technology is used in the luminescent layer. The fluorescent host material of the luminescent layer may be selected from, but not limited to one or more compounds listed in TDH1 to TDH24.
##STR00382## ##STR00383## ##STR00384## ##STR00385##
[0146] The OLED organic layer may further include an electron transport region between the luminescent layer and the cathode. The electron transport region may be an electron transport layer (ETL) with a single-layer structure, including a single-layer ETL only containing a compound and a single-layer ETL containing a plurality of compounds. The electron transport region also may be a multilayered structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL) and an electron blocking layer (EBL).
[0147] In one aspect of the present invention, the electron transport layer material may be selected from, but not limited to one or more combinations listed in ET-1 to ET-57.
##STR00386## ##STR00387## ##STR00388## ##STR00389## ##STR00390## ##STR00391## ##STR00392## ##STR00393## ##STR00394## ##STR00395## ##STR00396## ##STR00397## ##STR00398## ##STR00399## ##STR00400## ##STR00401##
[0148] The device may further include an electron injection layer located between the electron transport layer and the cathode, and the electron injection layer material includes, but not limited to one or more combinations listed below: LiQ, LiF, NaCl, CsF, Li.sub.2O, Cs.sub.2CO.sub.3, BaO, Na, Li or Ca.
Preparation Method of the Compound of the Present Invention
[0149] The synthetic method of the compound of the present invention will be described briefly with detailed synthetic embodiments below.
[0150] The solvents and reagents used in the following synthetic examples, for example, aryl brominated compounds, 2-bromo-9,9′-dimethyl fluorene, 2-bromo-dibenzofuran, 2-bromo-dibenzothiophene, 4-bromo-biphenyl, 4-cyclohexyl bromobenzene, 4-(4′-cyclohexyl phenyl) bromobenzene, tri(dibenzylidene acetone) dipalladium, 1,3-bis(2,6-diisopropylphenyl) imidazolium chloride, toluene, tetrahydrofuran, petroleum ether, n-hexane, dichloromethane, acetone, sodium sulfate, ethyl acetate, ethanol, acetic acid, potassium phosphate, tri-tert-butylphosphine, potassium/sodium tert-butoxide, phenylamine, 1-naphthylamine, 2-naphthylamine, 2-aminobiphenyl, 2-amino-4-methoxy-5′-methoxy-1,2′-dinaphthalene, 2-amino-1,2′-dinaphthalene, 2-amino-4-methoxy-5′-methoxy-1,1′-dinaphthalene, 2-amino-1,1′-dinaphthalene, [1,1′-bis (diphenylphosphine)ferrocene] palladium dichloride, triphenylphosphine, and other chemical reagents may be purchased or customized from domestic chemical product markets, for example, purchased from Sinopharm Chemical Reagent Co., Ltd, Shanghai Titan Scientific Co., Ltd., XILONG Chemical Industry Co, Ltd, Sigma-Aldrich and J&K Reagent Company. Moreover, intermediates are customized by reagent companies, and a person skilled in the art also may synthesize intermediates by a commonly known method.
[0151] Representative synthesis path of the compound of Formula (I) of the present invention is as follows, but the synthetic method of the compound of the present invention is not limited thereto.
##STR00402##
[0152] where, m, n, R.sup.1, R.sup.2, L.sup.1, L.sup.2, L.sup.3, Ar.sup.1, Ar.sup.2 and Ar.sup.3 and symbols in the Formula (I) have the same meaning.
[0153] More specifically, the following synthesis examples of the present invention exemplarily provide a detailed synthetic method of the representative compounds. It is confirmed that the mass spectrometer used in the following compounds is a ZAB-HS mass spectrometer for determination (manufactured by Britain Micromass).
Synthesis of the Compounds of Preferred Embodiment 1
Synthesis Example 1-1: Synthesis of the Compound P1
[0154] ##STR00403##
[0155] 13.5 g (50 mmol) M1, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M1-1.
[0156] 23 g (50 mmol) M1-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 mL tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P1.
[0157] M/Z theoretical value: 619; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 620.
Synthesis Example 1-2: Synthesis of the Compound P3
[0158] ##STR00404##
[0159] 13.5 g (50 mmol) M1, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M1-1.
[0160] 23 g (50 mmol) M1-1, 16 g (100 mmol) 4-(4-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P3.
[0161] M/Z theoretical value: 695; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 696.
Synthesis Example 1-3: Synthesis of the Compound P11
[0162] ##STR00405##
[0163] 13.5 g (50 mmol) M1, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M1-1.
[0164] 23 g (50 mmol) M1-1, 16 g (100 mmol) 2-cyclohexyl-4 phenylbromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P11.
[0165] M/Z theoretical value: 695; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 696.
Synthesis Example 1-4: Synthesis of the Compound P31
[0166] ##STR00406##
[0167] 13.5 g (50 mmol) M1, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M1-1.
[0168] 23 g (50 mmol) M1-1, 20 g (100 mmol) 2-phenyl-4(4′4-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P31.
[0169] M/Z theoretical value: 771; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 772.
Synthesis Example P1-5: Synthesis of the Compound P37
[0170] ##STR00407##
[0171] 13.5 g (50 mmol) M1, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M1-2.
[0172] 23 g (50 mmol) M1-2, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P37.
[0173] M/Z theoretical value: 619; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 620.
Synthesis Example 1-6: Synthesis of the Compound P39
[0174] ##STR00408##
[0175] 13.5 g (50 mmol) M1, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M1-2.
[0176] 23 g (50 mmol) M1-2, 16 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P39.
[0177] M/Z theoretical value: 695; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 696.
Synthesis Example 1-7: Synthesis of the Compound P61
[0178] ##STR00409##
[0179] 16.5 g (50 mmol) M2, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M2-1.
[0180] 26.5 g (50 mmol) M2-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P61.
[0181] M/Z theoretical value: 685; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 686.
Synthesis Example 1-8: Synthesis of the Compound P62
[0182] ##STR00410##
[0183] 16.5 g (50 mmol) M2, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M2-1.
[0184] 26.5 g (50 mmol) M2-1, 16 g (100 mmol) 4-(4,-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P62.
[0185] M/Z theoretical value: 762; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 763.
Synthesis Example 1-9: Synthesis of the Compound P73
[0186] ##STR00411##
[0187] 13.5 g (50 mmol) M3, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M3-1.
[0188] 23 g (50 mmol) M3-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 mL tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P73.
[0189] M/Z theoretical value: 619; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 620.
Synthesis Example 1-10: Synthesis of the Compound P75
[0190] ##STR00412##
[0191] 13.5 g (50 mmol) M3, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M3-1.
[0192] 23 g (50 mmol) M3-1, 16 g (100 mmol) 4-(4,-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P75.
[0193] M/Z theoretical value: 695; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 696.
Synthesis Example 1-11: Synthesis of the Compound P97
[0194] ##STR00413##
[0195] 15.5 g (50 mmol) M4, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M4-1.
[0196] 25 g (50 mmol) M4-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P97.
[0197] M/Z theoretical value: 659; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 660.
Synthesis Example 1-12: Synthesis of the Compound P109
[0198] ##STR00414##
[0199] 16.2 g (50 mmol) M5, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M5-1.
[0200] 26 g (50 mmol) M5-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P109.
[0201] M/Z theoretical value: 675; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 676.
Synthesis Example 1-13: Synthesis of the Compound P121
[0202] ##STR00415##
[0203] 19.5 g (50 mmol) M6, 13.6 g (50 mmol) 3-bromo-9,9-dimethyfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M6-1.
[0204] 29 g (50 mmol) M6-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P121.
[0205] M/Z theoretical value: 734; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 735.
Synthesis Example 1-14: Synthesis of the Compound P133
[0206] ##STR00416##
[0207] 19.5 g (50 mmol) M7, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M7-1.
[0208] 29 g (50 mmol) M7-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P133.
[0209] M/Z theoretical value: 734; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 735.
Synthesis Example 1-15: Synthesis of the Compound P173
[0210] ##STR00417##
[0211] 13.5 g (50 mmol) M8, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely. Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M8-1.
[0212] 23 g (50 mmol) M8-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P173.
[0213] M/Z theoretical value: 619; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 620.
Synthesis Example 1-16: Synthesis of the Compound P189
[0214] ##STR00418##
[0215] 13.5 g (50 mmol) M8, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M8-1.
[0216] 23 g (50 mmol) M8-1, 20 g (100 mmol) 2-phenyl-4-(4′-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P189.
[0217] M/Z theoretical value: 771; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 772.
Synthesis Example 1-17: Synthesis of the Compound P198
[0218] ##STR00419##
[0219] 15.5 g (50 mmol) M9, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M9-1.
[0220] 25 g (50 mmol) M9-1, 16 g (100 mmol) 4-(4′-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P198.
[0221] M/Z theoretical value: 735; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 736.
Synthesis Example 1-18: Synthesis of the Compound P209
[0222] ##STR00420##
[0223] 16 g (50 mmol) M10, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M10-1.
[0224] 26 g (50 mmol) M10-1, 12 g (100 mmol) 4-(4,-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL methylbenzene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P209.
[0225] M/Z theoretical value: 675; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 676.
Synthesis Example 1-19: Synthesis of the Compound P224
[0226] ##STR00421##
[0227] 19 g (50 mmol) M11, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M11-1.
[0228] 29 g (50 mmol) M11-1, 16 g (100 mmol) 2-phenyl-4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P224.
[0229] M/Z theoretical value: 810; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 811.
Synthesis Example 1-20: Synthesis of the Compound P229
[0230] ##STR00422##
[0231] 19 g (50 mmol) M12, 16 g (50 mmol) 4-(4-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely. Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M12-1.
[0232] 31 g (50 mmol) M12-1, 12 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P229.
[0233] M/Z theoretical value: 776; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 777.
Synthesis Example 1-21: Synthesis of the Compound P269
[0234] ##STR00423##
[0235] 16 g (50 mmol) M13, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M13-1.
[0236] 26.5 g (50 mmol) M13-1, 12 g (100 mmol) 4-(4,-cyclohexyl phenyl) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P269.
[0237] M/Z theoretical value: 685; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 686.
Synthesis Example 1-22: Synthesis of the Compound P179
[0238] ##STR00424##
[0239] 13.5 g (50 mmol) M8, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow M8-1.
[0240] 23 g (50 mmol) M8-1, 16.5 g (100 mmol) 1-cyclohexyl-4-bromodibenzofuran, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P179.
[0241] M/Z theoretical value: 709; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 710.
Synthesis Example 1-23: Synthesis of the Compound P287
[0242] ##STR00425##
[0243] 26 g (50 mmol) M15, 24 g (100 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P287.
[0244] M/Z theoretical value: 839; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 840.
Synthesis Example 1-24: Synthesis of the Compound P42
[0245] ##STR00426##
[0246] 17 g (50 mmol) M16, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M16-1.
[0247] 27 g (50 mmol) M16-1, 12 g (50 mmol) 4-bromobiphenyl, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P42.
[0248] M/Z theoretical value: 695; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 696.
Synthesis Example 1-25: Synthesis of the Compound P278
[0249] ##STR00427##
[0250] 11 g (50 mmol) M17, 13.6 g (50 mmol) 3-bromo-9,9-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g IPr.HCl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder M17-1.
[0251] 21 g (50 mmol) M17-1, 12 g (50 mmol) 4-cyclohexyl bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 g tri-tert-butylphosphine ((t-Bu).sub.3P), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder P278.
[0252] M/Z theoretical value: 569; ZAB-HS mass spectrometer (manufactured by Britain Micromass); M/Z measured value: 570.
Synthesis of the Compounds of Preferred Embodiment II
[0253] In this present invention, the synthetic method of the compound is described briefly, and the representative synthetic route of the compound is as follows:
##STR00428##
[0254] Based on the synthetic route and idea of the above compound, a person skilled in the art may obtain a compound having substituents of Ar.sup.1, Ar.sup.2, R.sup.1 and R.sup.2.
Synthesis Example 2-1: Synthesis of the Compound N1
[0255] ##STR00429##
[0256] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 15.7 g (100 mmol) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N1; M/Z theoretical value: 421, and M/Z measured value: 422.
Synthesis Example 2-2: Synthesis of the Compound N13
[0257] ##STR00430##
[0258] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 8.5 g (50 mmol) 2-methylbromobenzene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride (Pd(dppf)Cl.sub.2), 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl (Sphos), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S0.
[0259] 18 g (50 mmol) S0, 9.5 g (50 mmol) p-bromophenyl methyl ether, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine (P(t-Bu).sub.3) toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction; solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N13; M/Z theoretical value: 465, M/Z measured value: 466.
Synthesis Example 2-3: Synthesis of the Compound N34
[0260] ##STR00431##
[0261] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 12 g (50 mmol) 2-bromobiphenyl, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride (Pd(dppf)Cl.sub.2), 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S0-1.
[0262] 21 g (50 mmol) S0-1, 12 g (50 mmol) p-bromobiphenyl, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine (P(t-Bu).sub.3) toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N34; M/Z theoretical value: 573, M/Z measured value: 574.
Synthesis Example 2-4: Synthesis of the Compound N63
[0263] ##STR00432##
[0264] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 27 g (100 mmol) 2-bromo-9,9′-dimethylfluorene, 0.9 g (1 mL) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.5 mL tri-tert-butylphosphine (P(t-Bu).sub.3), 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide (NaOBu-t) were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N63; M/Z theoretical value: 653, and M/Z measured value: 654.
Synthesis Example 2-5: Synthesis of the Compound N93
[0265] ##STR00433##
[0266] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride (Pd(dppf)Cl.sub.2), 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0267] 23 g (50 mmol) Si, 16.1 g (50 mmol) 4-(4-bromo-phenyl)-dibenzofuran, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine (P(t-Bu).sub.3) toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N93; M/Z theoretical value: 703, M/Z measured value: 704.
Synthesis Example 2-6: Synthesis of the Compound N94
[0268] ##STR00434##
[0269] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethyfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0270] 23 g (50 mmol) S1, 16.1 g (50 mmol) 3-(4-bromo-phenyl)-dibenzofuran, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N94; M/Z theoretical value: 703, M/Z measured value: 704.
Synthesis Example 2-7: Synthesis of the Compound N100
[0271] ##STR00435##
[0272] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 10.3 g (50 mmol) 2-bromonaphthalene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S2.
[0273] 23 g (50 mmol) S2, 8.3 g (50 mmol) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, the reaction was terminated. Solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N100; M/Z theoretical value: 471. M/Z measured value: 472.
Synthesis Example 2-7: Synthesis of the Compound N120
[0274] ##STR00436##
[0275] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13 g (50 mmol) 9-bromophenanthrene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride (Pd(dppf)Cl.sub.2), 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S0-2.
[0276] 22 g (50 mmol) S0-2, 15 g (50 mmol) 3,5-diphenylbromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine (P(t-Bu).sub.3) toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N120; M/Z theoretical value: 673, M/Z measured value: 674.
Synthesis Example 2-9: Synthesis of the Compound N134
[0277] ##STR00437##
[0278] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0279] 23 g (50 mmol) S1, 11.5 g (50 mmol) 3-bromo-biphenyl, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N134; M/Z theoretical value: 613, M/Z measured value: 614.
Synthesis Example 2-10: Synthesis of the Compound N147
[0280] ##STR00438##
[0281] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0282] 23 g (50 mmol) S1, 10.4 g (50 mmol) 2-bromonaphthalene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N147; M/Z theoretical value: 587, M/Z measured value: 588.
Synthesis Example 2-11: Synthesis of the Compound N170
[0283] ##STR00439##
[0284] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 27 g (100 mmol) 3-bromo-9,9′-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone)dipalladium, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N170; M/Z theoretical value: 653, and M/Z measured value: 654.
Synthesis Example 2-12: Synthesis of the Compound N176
[0285] ##STR00440##
[0286] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0287] 23 g (50 mmol) S1, 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N176; M/Z theoretical value: 653, M/Z measured value: 654.
Synthesis Example 2-13: Synthesis of the Compound N191
[0288] ##STR00441##
[0289] 13.5 g (50 mmol) 2-amino-1,2′-dinaphthalene, 15.7 g (100 mmol) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N191; M/Z theoretical value: 421, and M/Z measured value: 422.
Synthesis Example 2-14: Synthesis of the Compound N314
[0290] ##STR00442##
[0291] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13 g (50 mmol) 9-bromoanthracene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride (Pd(dppf)Cl.sub.2), 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S0-3.
[0292] 22 g (50 mmol) S0-3, 15 g (50 mmol) 3,5-diphenylbromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine (P(t-Bu).sub.3) toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N314; M/Z theoretical value: 673, M/Z measured value: 674.
Synthesis Example 2-15: Synthesis of the Compound N325
[0293] ##STR00443##
[0294] 13.5 g (50 mmol) 2-amino-1,2′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S2.
[0295] 23 g (50 mmol) S1, 11.5 g (50 mmol)3-bromo-biphenyl, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N325; M/Z theoretical value: 613, M/Z measured value: 614.
Synthesis Example 2-16: Synthesis of the Compound N331
[0296] ##STR00444##
[0297] 13.5 g (50 mmol) 2-amino-1,2′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S2.
[0298] 23 g (50 mmol) S2, 12.3 g (50 mmol) 2-bromo-dibenzofuran, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N331; M/Z theoretical value: 627, M/Z measured value: 628.
Synthesis Example 2-17: Synthesis of the Compound N337
[0299] ##STR00445##
[0300] 13.5 g (50 mmol) 2-amino-1,2′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S2.
[0301] 23 g (50 mmol) S2, 10.4 g (50 mmol) 2-bromonaphthalene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N337; M/Z theoretical value: 587, M/Z measured value: 588.
Synthesis Example 2-18: Synthesis of the Compound N371
[0302] ##STR00446##
[0303] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 32.2 g (100 mmol) 9-(4-bromophenyl)-carbazole, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N371; M/Z theoretical value: 751, and M/Z measured value: 752.
Synthesis Example 2-19: Synthesis of the Compound N372
[0304] ##STR00447##
[0305] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 32.2 g (100 mmol) 9-(3-bromophenyl-carbazole, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N372; M/Z theoretical value: 751, and M/Z measured value: 752.
Synthesis Example 2-20: Synthesis of the Compound N373
[0306] ##STR00448##
[0307] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 30.9 g (100 mmol) 3-bromoterphenyl, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N373; M/Z theoretical value: 725, and M/Z measured value: 726.
Synthesis Example 2-21: Synthesis of the Compound N374
[0308] ##STR00449##
[0309] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 24.5 g (100 mmol) 4-bromodibenzofuran, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N374; M/Z theoretical value: 601.31, and M/Z measured value: 602.
Synthesis Example 2-22: Synthesis of the Compound N375
[0310] ##STR00450##
[0311] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 32.3 g (100 mmol) 4-(4-bromophenyl)-dibenzofuran, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N375; M/Z theoretical value: 753, and M/Z measured value: 754.
Synthesis Example 2-23: Synthesis of the Compound N376
[0312] ##STR00451##
[0313] 13.5 g (50 mmol) 2-amino 0.5 mL-1,1′-dinaphthalene, 10 g (100 mmol) 2-bromonaphthalene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N376; M/Z theoretical value: 521, and M/Z measured value: 522.
Synthesis Example 2-24: Synthesis of the Compound N377
[0314] ##STR00452##
[0315] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 32.2 g (100 mmol) (9-phenyl)-3-bromocarbazole, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N377; M/Z theoretical value: 751, and M/Z measured value: 752.
Synthesis Example 2-25: Synthesis of the Compound N378
[0316] ##STR00453##
[0317] 6.7 g (25 mmol) 2-amino-1,1′-dinaphthalene, 20 g (100 mmol) 4-bromo-9,9′-spirobifluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N378; M/Z theoretical value: 898, and M/Z measured value: 898.
Synthesis Example 2-26: Synthesis of the Compound N379
[0318] ##STR00454##
[0319] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0320] 23 g (50 mmol) S1, 32.2 g (100 mmol) 9-(4-bromophenyl)-carbazole, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N379; M/Z theoretical value: 702, M/Z measured value: 703.
Synthesis Example 2-27: Synthesis of the Compound N380
[0321] ##STR00455##
[0322] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0323] 23 g (50 mmol) S1, 32.2 g (100 mmol) 9-(3-bromophenyl)-carbazole, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, the reaction was terminated. Solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N380; M/Z theoretical value: 702, M/Z measured value: 703.
Synthesis Example 2-28: Synthesis of the Compound N381
[0324] ##STR00456##
[0325] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0326] 23 g (50 mmol) S1, 16.1 g (100 mmol) (9-phenyl)-3-bromocarbazole, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N381; M/Z theoretical value: 702, M/Z measured value: 703.
Synthesis Example 2-29: Synthesis of the Compound N382
[0327] ##STR00457##
[0328] 13.5 g (50 mmol) 2-amino-4-methoxy-5′-methoxy-1,1′-dinaphthalene, 27 g (100 mmol) 2-bromo-9,9′-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 0.5 mL tri-tert-butylphosphine, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder N382; M/Z theoretical value: 713, and M/Z measured value: 714.
Synthesis Example 2-30: Synthesis of the Compound N383
[0329] ##STR00458##
[0330] 13.5 g (50 mmol) 2-amino-4-methoxy-5′-methoxy-1,2′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S2.
[0331] 23 g (50 mmol) S2, 12.3 g (50 mmol) 2-bromo-dibenzofuran, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, the reaction was terminated. Solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N383; M/Z theoretical value: 687, M/Z measured value: 688.
Synthesis Example 2-31: Synthesis of the Compound N387
[0332] ##STR00459##
[0333] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 2-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S1.
[0334] 23 g (50 mmol) S1, 13.5 g (100 mmol) 3-bromo-9,9′-dimethylfluorene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N387; M/Z theoretical value: 653, M/Z measured value: 654.
Synthesis Example 2-32: Synthesis of the Compound N389
[0335] ##STR00460##
[0336] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 3-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S4.
[0337] 23 g (50 mmol) S4, 12 g (100 mmol) p-bromo-biphenyl, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 11000 for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N389; M/Z theoretical value: 633, M/Z measured value: 634.
Synthesis Example 2-33: Synthesis of the Compound N396
[0338] ##STR00461##
[0339] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 3-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S4.
[0340] 23 g (50 mmol) S4, 10.5 g (100 mmol) 2-bromonaphthalene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N396; M/Z theoretical value: 587, M/Z measured value: 588.
Synthesis Example 2-34: Synthesis of the Compound N405
[0341] ##STR00462##
[0342] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 3-bromo-9,9′-dimethyfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S4.
[0343] 23 g (50 mmol) S4, 8.7 g (100 mmol) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N405; M/Z theoretical value: 537, M/Z measured value: 538.
Synthesis Example 2-35: Synthesis of the Compound N406
[0344] ##STR00463##
[0345] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 3-bromo-9,9′-dimethyfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S4.
[0346] 23 g (50 mmol) S4, 12 g (100 mmol) 2-bromobiphenyl, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N406; M/Z theoretical value: 613, M/Z measured value: 614.
Synthesis Example 2-36: Synthesis of the Compound N409
[0347] ##STR00464##
[0348] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 3-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S4.
[0349] 23 g (50 mmol) S4, 17.5 g (100 mmol) 3-(2-(9,9-dimethylfluorene)) bromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N409; M/Z theoretical value: 729, M/Z measured value: 730.
Synthesis Example 2-37: Synthesis of the Compound N414
[0350] ##STR00465##
[0351] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 3-bromo-9,9′-dimethylfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S4.
[0352] 23 g (50 mmol) S4, 15 g (100 mmol) 3,5-diphenylbromobenzene, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N414; M/Z theoretical value: 689, M/Z measured value: 690.
Synthesis Example 2-38: Synthesis of the Compound N418
[0353] ##STR00466##
[0354] 13.5 g (50 mmol) 2-amino-1,1′-dinaphthalene, 13.5 g (50 mmol) 3-bromo-9,9′-dimethyfluorene, 0.7 g (1 mmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride, 0.5 g 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl, 500 mL toluene, and 14.4 g (150 mmol) sodium tert-butoxide were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 5 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then methanol was added and stirred for 1 h, and suction filtration was performed to obtain a faint yellow powder S4.
[0355] 23 g (50 mmol) S4, 15 g (100 mmol) 2-phenyl-1-bromo-biphenyl, 0.9 g (1 mmol) tri(dibenzylidene acetone) dipalladium, 500 mL toluene were added to a 1000 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, and 0.5 mL tri-tert-butylphosphine toluene solution was added, and heated up to 110° C. for reaction for 12 h; at the end of the reaction, solvent was removed by evaporation, and silica-gel column chromatography was performed to obtain N418; M/Z theoretical value: 689, M/Z measured value: 690.
Synthesis of the Compounds of Preferred Embodiment III
[0356] The synthetic routes of the compounds as shown in the Formulas (III-1), (III-2) and (III-3) of the present invention are as follows:
##STR00467## ##STR00468## ##STR00469##
[0357] Multiple synthesis examples are set as examples below to describe the specific preparation methods of the above novel compounds of the present invention, but the preparation methods of the present invention are not limited to these synthesis examples.
Synthesis Example 3-1: Synthesis of the Compound T1
[0358] ##STR00470##
[0359] 15 g (55.69 mmol) compound P, 18 g (55.69 mmol) 3-bromo-11,11-dimethyl-benzfluorene, 0.4 g (556.92 μmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride (namely, Pd(dppf)Cl.sub.2), 0.45 g (1.1 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl (namely, sphos), 200 mL toluene, and 16.06 g (167.08 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 12 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, and silica-gel column chromatography was performed to obtain a compound PM. M/Z theoretical value: 511; M/Z measured value: 512.
[0360] 20 g (39.09 mmol) compound PM, 7.9 g (50.82 mmol) bromobenzene, 0.71 g (781.78 μmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.64 g (1.56 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxy biphenyl, 300 mL toluene and 11.27 g (117.27 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 10 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then silica-gel column chromatography was performed to obtain a compound T1.M/Z theoretical value: 587; M/Z measured value: 588.
Synthesis Example 3-2: Synthesis of the Compound T2
[0361] ##STR00471##
[0362] 20 g (39.09 mmol) compound PM, 11.85 g (50.82 mmol) 4-bromobiphenyl, 0.71 g (781.78 μmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.64 g (1.56 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxy biphenyl (namely, sphos) 300 mL toluene and 11.27 g (117.27 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 10 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then silica-gel column chromatography was performed to obtain a compound T2.M/Z theoretical value: 663; M/Z measured value: 664.
Synthesis Example 3-3: Synthesis of the Compound T11
[0363] ##STR00472##
[0364] 20 g (39.09 mmol) compound PM, 13.07 g (50.82 mmol) 9-bromophenanthrene, 0.71 g (781.78 μmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.64 g (1.56 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxy biphenyl (namely, sphos) 300 mL toluene and 11.27 g (117.27 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 10 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then silica-gel column chromatography was performed to obtain a compound T11.M/Z theoretical value: 687; M/Z measured value: 688.
Synthesis Example 3-4: Synthesis of the Compound T12
[0365] ##STR00473##
[0366] 20 g (39.09 mmol) compound PM, 8.69 g (50.82 mmol) 1-bromo-4-methylbenzene, 0.71 g (781.78 μmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.64 g (1.56 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxy biphenyl (namely, sphos) 300 mL toluene and 11.27 g (117.27 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 10 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then silica-gel column chromatography was performed to obtain a compound T12.M/Z theoretical value: 601; M/Z measured value: 602.
Synthesis Example 3-5: Synthesis of the Compound T81
[0367] ##STR00474##
[0368] 15 g (55.69 mmol) compound P, 18 g (55.69 mmol) 2-bromo-11,11-dimethyl-benzfluorene, 0.4 g (556.92 μmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride (namely, Pd(dppf)Cl.sub.2), 0.45 g (1.1 mmol) 2-biyclohexylphosphine-2′,6′-dimethoxybiphenyl (namely, sphos), 200 mL toluene, and 16.06 g (167.08 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 12 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, and silica-gel column chromatography was performed to obtain a compound PN.M/Z theoretical value: 511; M/Z measured value: 512.
[0369] 20 g (39.09 mmol) compound PM, 13.37 g (50.82 mmol) 4-bromodibenzothiophene, 0.71 g (781.78 μmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.64 g (1.56 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxy biphenyl (namely, sphos) 300 mL toluene and 11.27 g (117.27 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 10 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then silica-gel column chromatography was performed to obtain a compound T81.M/Z theoretical value: 693; M/Z measured value: 694.
Synthesis Example 3-6: Synthesis of the Compound T163
[0370] ##STR00475##
[0371] 15 g (55.69 mmol) compound PA, 18 g (55.69 mmol) 4-bromo-11,11-dimethyl-benzfluorene, 0.4 g (556.92 μmol) [1,1′-bis(diphenylphosphine)ferrocene] palladium dichloride (namely, Pd(dppf)Cl.sub.2), 0.45 g (1.1 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxybiphenyl (namely, sphos), 200 mL toluene, and 16.06 g (167.08 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 90° C. for reacting for 12 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, and silica-gel column chromatography was performed to obtain a compound PN.M/Z theoretical value: 511; M/Z measured value: 512.
[0372] 20 g (39.09 mmol) compound PQ, 11.85 g (50.82 mmol) m-bromotoluene, 0.71 g (781.78 μmol) tri(dibenzylidene acetone) dipalladium (namely. Pd.sub.2(dba).sub.3), 0.64 g (1.56 mol) 2-bicyclohexylphosphine-2′,6′-dimethoxy biphenyl (namely, sphos) 300 mL toluene and 11.27 g (117.27 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 10 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then silica-gel column chromatography was performed to obtain a compound T163.M/Z theoretical value: 663; M/Z measured value: 664.
Synthesis Example 3-7: Synthesis of the Compound T170
[0373] ##STR00476##
[0374] 20 g (39.09 mmol) compound PQ, 10.52 g (50.82 mmol) 2-bromonaphthalene, 0.71 g (781.78 μmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.64 g (1.56 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxy biphenyl (namely, sphos) 300 mL toluene and 11.27 g (117.27 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 10 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then silica-gel column chromatography was performed to obtain a compound T170.M/Z theoretical value: 637; M/Z measured value: 638.
Synthesis Example 3-8: Synthesis of the Compound T232
[0375] ##STR00477##
[0376] 20 g (39.09 mmol) compound PQ, 16.42 g (50.82 mmol) 4-(4-bromophenyl-dibenzofuran, 0.71 g (781.78 μmol) tri(dibenzylidene acetone) dipalladium (namely, Pd.sub.2(dba).sub.3), 0.64 g (1.56 mmol) 2-bicyclohexylphosphine-2′,6′-dimethoxy biphenyl (namely, sphos) 300 mL toluene and 11.27 g (117.27 mmol) sodium tert-butoxide (NaOBu-t) were added to a 500 mL single-necked flask, and vacuumized for nitrogen exchange for 3 times, then the reaction was heated up to 110° C. for reacting for 10 h. The reaction was terminated at the end of the reaction. The flask was cooled to room temperature, and reaction liquid was separated, and organic phases were concentrated, then silica-gel column chromatography was performed to obtain a compound T232. M/Z theoretical value: 753; M/Z measured value: 754.
[0377] The compounds of the present invention will be specifically applied in an organic electroluminescent device to test actual operational performance to display and verify the technical effects and advantages of the present invention.
Devices Utilizing the Compounds of Preferred Embodiment I
Example 1-1
[0378] This example provides an organic electroluminescent device, and the specific preparation process is as follows:
[0379] a glass pane coated with an ITO transparent conducting layer was subjected to ultrasonic treatment in a commercial detergent, washed in deionized water, and subjected to ultrasonic degreasing in a mixed solvent of acetone: ethanol, and baked in a clean environment till water content was removed completely; then washed with UV-light and ozone, and the surface thereof was bombarded with a low-energy cationic beam;
[0380] the above glass substrate with an anode was put to a vacuum chamber, and vacuumized to be less than 1×10.sup.−5 Pa; the above anode coating film was evaporated with an HT-4:HI-3 (97/3, w/w) mixture under vacuum as a hole injection layer, where the evaporation rate was 0.1 nm/s and the evaporation coating thickness was 10 nm;
[0381] HT-4 was evaporated above the hole injection layer under vacuum as a hole transport layer of the device, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 60 nm;
[0382] the compound p1 synthesized in the synthesis example 1-1 was evaporated above the hole transport layer under vacuum as an electron blocking layer material of the device, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 60 nm;
[0383] a luminescent layer was evaporated above the electron blocking layer under vacuum; the luminescent layer includes a host material and a dyeing material; a multi-source co-evaporation method was used to adjust the evaporation rate of the host material GPH-59 to 0.1 nm/s; the evaporation rate of the dye RPD-8 was set by a ratio of 3%, and the total evaporation coating thickness was 40 nm;
[0384] an electron transport layer (material: ET-46) was evaporated above the luminescent layer under vacuum, and set by a ratio of 50%, and ET-57 was set by a ratio of 50%, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 25 nm:
[0385] LF with a thickness of 0.5 nm, as an electron injection layer, was evaporated above the electron transport layer (ETL) under vacuum and an Al layer with a thickness of 150 nm served as a cathode of the device.
Examples 1-2 to 1-25
[0386] The preparing process of Examples 1-2 to 1-25 is the same that in Example 1-1, and what is different is that the compound P1 of the electron blocking layer material is respectively replaced with the compounds as shown in Table 1.
Comparative Examples 1-1 to 1-2
[0387] The preparing process of Comparative Examples 1-1 to 1-2 is the same that in Example 1-1, and what is different is that the compound P1 of the electron blocking layer material is respectively replaced with the compounds R-1 and R-2; the compound used in Comparative Examples 1-1 to 1-2 has the following structure:
##STR00478##
[0388] performance measurement is performed on the organic electroluminescent device prepared by the above process below:
[0389] (1) at a same luminance value, a digital source-meter (Keithley2400) and a luminance meter (ST-86LA luminance meter, Beijing Normal University Photoelectric Instrument Plant) were used to measure the driving voltage, current efficiency and service life of the organic electroluminescent device prepared in Examples 1-1 to 1-25 and Comparative Examples 1-1 to 1-2. Specifically, voltage was increased at a rate of 0.1V/s, when the luminance of the organic electroluminescent device was up to 5000 cd/m.sup.2, the voltage was measured as the driving voltage, and electric current density was measured at this time simultaneously; the ratio of the luminance to the electric current density was the current efficiency;
[0390] (2) life test of LT95 was as follows: a luminance meter was used to keep a constant current under a luminance value of 5000 cd/m.sup.2; the time when the luminance of the organic electroluminescent device dropped to 4750 cd/m.sup.2 was measured with a unit of hour.
[0391] The test results were shown in table 1.
TABLE-US-00001 TABLE 1 Desired Current Hole-transport luminance Voltage efficiency layer material cd/m V cd/A Comparative R-1 5000.00 5.3 10.2 Example 1-1 Comparative R-2 5000.00 5.8 8.9 Example 1-2 Example 1-1 P1 5000.00 4.8 15 Example 1-2 P3 5000.00 4.6 16.2 Example 1-3 P11 5000.00 4.6 16.7 Example 1-4 P31 5000.00 5.0 13 Example 1-5 P37 5000.00 4.7 15 Example 1-6 P39 5000.00 4.7 14.2 Example 1-7 P42 5000.00 4.8 13.2 Example 1-8 P61 5000.00 4.6 17.1 Example 1-9 P62 5000.00 4.7 12.8 Example 1-10 P73 5000.00 4.8 16.4 Example 1-11 P75 5000.00 4.9 14.7 Example 1-12 P97 5000.00 4.8 18 Example 1-13 P109 5000.00 4.6 15.6 Example 1-14 P121 5000.00 4.7 16.9 Example 1-15 P133 5000.00 4.7 14.5 Example 1-16 P173 5000.00 4.8 16.1 Example 1-17 P179 5000.00 4.9 15.4 Example 1-18 P189 5000.00 4.8 14 Example 1-19 P198 5000.00 4.5 15.3 Example 1-20 P209 5000.00 4.9 15.5 Example 1-21 P224 5000.00 4.6 14.5 Example 1-22 P229 5000.00 4.6 14.8 Example 1-23 P269 5000.00 4.9 15.8 Example 1-24 P278 5000.00 4.9 13.8 Example 1-25 P287 5000.00 5.0 14.1
[0392] It can be seen from the results of Table 1 that when the compounds of the present invention are used as the hole-transport material of the organic electroluminescent device, and when the luminance is up to 5000 cd/m.sup.2, the driving voltage is as low as 5.0 V below, and the current efficiency is up to 12.8 cd/A above; compared with the Comparative Examples 1-1 to 1-2, the compounds the present invention may effectively reduce the driving voltage, improve the current efficiency and thus, is a kind of electron blocking material with good performances. The reason has been not clear, but it is presumed as follows: compared with the compound R-1 of Comparative Example 1-1, when the compounds in Examples 1-1 to 1-25 of the present invention are used as the electron blocking material of the organic electroluminescent device, because there is a cycloalkyl group substituted in a specific position and there is an aromatic substituent in an orthortho position of amido on a naphthalene ring, molecules may be promoted to be spread out on a plane of the device, which induces the subsequently deposited molecules on the luminescent layer also to be piled in such a plane space way. The luminescent molecules piled in a spreading way are beneficial to the improvement of optical extraction efficiency, thereby promoting the current efficiency. Due to lack of an aromatic substituent in the orthortho position of amido only, the compound R-2 used in the Comparative Example 1-2 may not achieve high efficiency, and the voltage is staying at a high level. Thus, it can be seen that the molecules may not achieve the beneficial molecular arrangement possessed by the compounds of the present invention. The above analysis is enough to show that the unique molecular structure of the compounds of the present invention, is the crucial to achieve the outstanding performance of the devices in the examples. When the luminance of the organic electroluminescent device utilizing the compounds of the present invention is up to 5000 cd/m.sup.2, the driving voltage is as low as 5.0 V and below, and the current efficiency is up to 12.8 cd/A and above, and LT95 is up to 21 h and above.
Devices Utilizing the Compounds of Preferred Embodiment II
Example 2-1
[0393] This example provides an organic electroluminescent device, and the specific preparation process is as follows:
[0394] a glass pane coated with an ITO transparent conducting layer was subjected to ultrasonic treatment in a commercial detergent, washed in deionized water, and subjected to ultrasonic degreasing in a mixed solvent of acetone: ethanol, and baked in a clean environment till water was removed completely; then washed with UV-light and ozone, and the surface was bombarded with a low-energy cationic beam;
[0395] the above glass substrate with an anode was put to a vacuum chamber, and vacuumized to be less than 1×10.sup.−5 Pa; the above anode coating film was evaporated with HI-3 under vacuum as a hole injection layer, where the evaporation rate was 0.1 nm/s and the evaporation coating thickness was 10 nm;
[0396] the compound N1 synthesized in the synthesis example 2-1 was evaporated above the hole injection layer under vacuum as a hole transport layer of the device, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 80 nm;
[0397] HT-14 was evaporated above the hole transport layer under vacuum as an electron blocking layer of the device, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 80 nm;
[0398] a luminescent layer of the device was evaporated above the electron blocking layer under vacuum; the luminescent layer includes a host material and a dyeing material; a multi-source co-evaporation method was used to adjust the evaporation rate of the host material GPH-59 to 0.1 nm/s; the evaporation rate of the dye RPD-8 was set by a ratio of 3%, and the total evaporation coating thickness was 30 nm;
[0399] an electron transport layer (material: ET-46) was evaporated above the luminescent layer under vacuum, and set by a ratio of 50%, and ET-57 was set by a ratio of 50%, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 30 nm;
[0400] LF with a thickness of 0.5 nm, as an electron injection layer, was evaporated above the electron transport layer (ETL) under vacuum, and an Al layer with a thickness of 150 nm served as a cathode of the device.
Examples 2-2 to 2-33 and Comparative Examples 2-1 to 2-4
[0401] The preparing process of Examples 2-2 to 2-33 and Comparative Examples 2-1 to 2-4 is the same that in Example 2-1, and what is different is that the compound N1 is replaced with the compounds as shown in Table 2, as the hole-transport material.
[0402] The hole-transport materials EMT-1 to EMT-4 in Comparative Examples 2-1 to 2-4 have the following structure:
##STR00479##
[0403] performance measurement is performed on the organic electroluminescent device prepared in Examples 2-1 to 2-33 and Comparative Examples 2-1 to 2-4 below:
[0404] at a same luminance value, a digital source-meter and a luminance meter were used to measure the driving voltage, current efficiency and service life of the organic electroluminescent device prepared in Examples 2-1 to 2-33 and Comparative Examples 2-1 to 2-4. Specifically, voltage was increased at a rate of 0.1 V/s, when the luminance of the organic electroluminescent device was up to 3000 cd/m.sup.2, the voltage was measured as the driving voltage, and electric current density was measured at this time simultaneously; the ratio of the luminance to the electric current density was the current efficiency; LTO5 life test was as follows: a luminance meter was used to keep a constant current under a luminance value of 5000 cd/m2; the time when the luminance of the organic electroluminescent device dropped to 4750 cd/m.sup.2 was measured with a unit of hour. The measured results were shown in table 2.
TABLE-US-00002 TABLE 2 hole- transport Desired Current Service layer luminance Voltage efficiency life material cd/m.sup.2 V cd/A (LT95) h Comparative EMT-1 3000 5.7 7.5 60 Example 2-1 Comparative EMT-2 3000 5.5 8.1 58 Example 2-2 Comparative EMT-3 3000 4.6 9.3 77 Example 2-3 Comparative EMT-4 3000 4.7 10.2 86 Example 2-4 Example 2-1 N1 3000 3.1 15 196 Example 2-2 N13 3000 3.4 13.5 201 Example 2-3 N34 3000 3.2 14.2 187 Example 2-4 N63 3000 3.5 13 200 Example 2-5 N93 3000 3.4 10.5 162 Example 2-6 N94 3000 3.2 16 230 Example 2-7 N100 3000 3.4 10.8 188 Example 2-8 N120 3000 3.2 13.6 195 Example 2-9 N134 3000 3.2 13.6 196 Example 2-10 N147 3000 3.1 12 200 Example 2-11 N170 3000 3.2 15 194 Example 2-12 N176 3000 3.2 16 210 Example 2-13 N191 3000 3.1 16.2 198 Example 2-14 N314 3000 3.3 15.1 231 Example 2-15 N325 3000 3.3 11 179 Example 2-16 N331 3000 3.3 14.5 185 Example 2-17 N337 3000 3.3 15.5 187 Example 2-18 N371 3000 3.1 16.3 163 Example 2-19 N372 3000 3.2 15.4 187 Example 2-20 N373 3000 3.2 16.2 213 Example 2-21 N374 3000 3.4 17.1 193 Example 2-22 N375 3000 3.1 14.8 152 Example 2-23 N376 3000 3.1 13.4 183 Example 2-24 N377 3000 3.2 18.4 178 Example 2-25 N378 3000 3.5 14.5 195 Example 2-26 N379 3000 3.3 14.1 164 Example 2-27 N380 3000 3.2 15 185 Example 2-28 N381 3000 3.1 14.7 178 Example 2-29 N382 3000 3.5 15.8 169 Example 2-30 N383 3000 3.1 16.1 186 Example 2-31 N387 3000 3.0 16 202 Example 2-32 N389 3000 3.1 18.3 197 Example 2-33 N396 3000 3.1 17.7 226
[0405] It can be seen from the results of Table 2 that when the compounds in Examples 2-1 to 2-33 of the present invention are used as the hole-transport material of the organic electroluminescent device, and when the luminance is up to 3000 cd/m.sup.2, the driving voltage is as low as 3.5 V below, and the current efficiency is up to 10.5 cd/A above; LT95 is up to 152 h above. Therefore, the compounds of the present invention may effectively reduce the driving voltage, improve the current efficiency and prolong the service life of the device, and thus is a kind of electron blocking material with good performances. In contrast to this, the organic electroluminescent devices, in which the compounds in Comparatives Examples 2-1 to 2-4 were used as hole-transport materials have different levels of shortages in driving voltage, current efficiency, service life and other aspects. The reason has been not clear, but it is presumed as follows: in the molecular structure of compounds EMT 1 and EMT-2 in Comparative Examples 2-1 and 2-2, R.sup.2 is arylamido; and in the molecular structure of compounds EMT-3 and EMT-4 in Comparative Examples 2-3 and 2-4, the arylamido on the naphthalene ring and naphthyl are not located in the orthortho position. Therefore, these compounds may not accord with the definition requirement of claim 1 and thus may not achieve the technical effect of the present invention.
Examples 2-34
[0406] This example provides an organic electroluminescent device, and the specific preparation process is as follows:
[0407] a glass pane coated with an ITO transparent conducting layer was subjected to ultrasonic treatment in a commercial detergent, washed in deionized water, and subjected to ultrasonic degreasing in a mixed solvent of acetone: ethanol, and baked in a clean environment till water was removed completely; then washed with UV-light and ozone, and the surface thereof was bombarded with a low-energy cationic beam;
[0408] the above glass substrate with an anode was put to a vacuum chamber, and vacuumized to be less than 1×10.sup.−5 Pa; the above anode coating film was evaporated with an HI-3 under vacuum as a hole injection layer, where the evaporation rate was 0.1 nm/s and the evaporation coating thickness was 10 nm;
[0409] HT-4 was evaporated above the hole injection layer under vacuum as a hole transport layer of the device, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 80 nm;
[0410] the compound N1 synthesized in the synthesis example 1 was evaporated above the hole transport layer under vacuum as an electron blocking layer of the device, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 80 nm;
[0411] a luminescent layer of the device was evaporated above the electron blocking layer under vacuum; the luminescent layer includes a host material and a dyeing material; and a multi-source co-evaporation method was used to adjust the evaporation rate of the host material GPH-59 to 0.1 nm/s; the evaporation rate of the dye RPD-8 was set by a ratio of 3%, and the total evaporation coating thickness was 30 nm;
[0412] an electron transport layer (material: ET-46) was evaporated above the luminescent layer under vacuum, and set by a ratio of 50%, and ET-57 was set by a ratio of 50%, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 30 nm;
[0413] LF with a thickness of 0.5 nm, as an electron injection layer, was evaporated above the electron transport layer (ETL) under vacuum r, and an Al layer with a thickness of 150 nm served as a cathode of the device.
Examples 2-35 to 2-71 and Comparative Examples 2-5 to 2-8
[0414] The preparing process of Examples 2-35 to 2-71 and Comparative Examples 2-5 to 2-8 is the same that in Example 2-34, and what is different is that the compound N1 is replaced with the compounds as shown in Table 3 as the hole-transport material.
[0415] Performance measurement is performed on the organic electroluminescent device prepared in Examples 2-34 to 2-71 and Comparative Examples 2-5 to 2-8 below:
[0416] at a same luminance value, a digital source-meter and a luminance meter were used to measure the driving voltage, current efficiency and service life of the organic electroluminescent device prepared in Examples 2-34 to 2-71 and Comparative Examples 2-5 to 2-8. Specifically, voltage was increased at a rate of 0.1 V/s, when the luminance of the organic electroluminescent device was up to 3000 cd/m.sup.2, the voltage was measured as the driving voltage, and electric current density was measured at this time simultaneously; the ratio of the luminance to the electric current density was the current efficiency; LT95 life test was as follows: a luminance meter was used to keep a constant current under a luminance value of 5000 cd/m.sup.2: the time when the luminance of the organic electroluminescent device dropped to 4750 cd/m.sup.2 was measured with a unit of hour. The measured results were shown in Table 3.
TABLE-US-00003 TABLE 3 Electron blocking Desired Current Service layer luminance Voltage efficiency life material cd/m.sup.2 V cd/A (LT95) h Comparative EMT-1 3000 5.6 7.6 66 Example 2-5 Comparative EMT-2 3000 5.4 8.9 93 Example 2-6 Comparative EMT-3 3000 5.0 8.2 87 Example 2-7 Comparative EMT-4 3000 5.3 8.5 70 Example 2-8 Examples 2-34 N1 3000 3.7 13 214 Examples 2-35 N13 3000 3.4 16.3 220 Examples 2-36 N34 3000 3.3 14.2 173 Examples 2-37 N63 3000 3.8 14 230 Examples 2-38 N93 3000 3.6 12.5 180 Examples 2-39 N94 3000 3.5 18 250 Examples 2-40 N100 3000 3.4 16 190 Examples 2-41 N120 3000 3.2 17 241 Examples 2-42 N134 3000 3.5 17.5 196 Examples 2-43 N147 3000 3.2 19 243 Examples 2-44 N170 3000 3.6 17 201 Examples 2-45 N176 3000 3.8 16.5 198 Examples 2-46 N191 3000 3.5 19 184 Examples 2-47 N314 3000 3.6 15.4 192 Examples 2-48 N325 3000 3.4 17 188 Examples 2-49 N331 3000 3.2 16.8 211 Examples 2-50 N337 3000 3.5 17.4 184 Examples 2-51 N371 3000 3.7 18.9 199 Examples 2-52 N372 3000 3.5 15.9 167 Examples 2-53 N373 3000 3.1 20 238 Examples 2-54 N374 3000 3.3 19 223 Examples 2-55 N375 3000 3.2 17 176 Examples 2-56 N376 3000 3.0 14 169 Examples 2-57 N377 3000 3.8 21 250 Examples 2-58 N378 3000 3.6 22 199 Examples 2-59 N379 3000 3.2 19.6 189 Examples 2-60 N380 3000 3.3 18 235 Examples 2-61 N381 3000 3.4 16.9 174 Examples 2-62 N382 3000 3.2 18 197 Examples 2-63 N383 3000 3.0 19 186 Examples 2-64 N387 3000 3.0 18.9 233 Examples 2-65 N389 3000 3.1 19.3 241 Examples 2-66 N396 3000 3.0 21 231 Examples 2-67 N405 3000 3.3 19 210 Examples 2-68 N406 3000 3.4 18.5 198 Examples 2-69 N409 3000 3.2 19.2 180 Examples 2-70 N414 3000 3.3 20 179 Examples 2-71 N418 3000 3.5 17.8 222
[0417] It can be seen from the results of Table 3 that when the compounds in Examples 2-34 to 2-71 of the present invention are used as the electron blocking layer materials of the organic electroluminescent device, and when the luminance is up to 3000 cd/m.sup.2, the driving voltage is as low as 3.8 V below, and the current efficiency is up to 12.5 cd/A above; LT95 is up to 167 h above. Therefore, the compounds of the present invention may effectively reduce the driving voltage, improve the current efficiency and thus, prolong the service life of the device, and thus is a kind of electron blocking material with good performances. In contrast to this, the organic electroluminescent devices in which the compounds in Comparatives Examples 2-5 to 2-8 were used as electron blocking layer materials, have different levels of shortages in driving voltage, current efficiency, service life and other aspects. The reason has been not clear, but it is presumed as follows: in the molecular structure of compounds EMT-1 and EMT-2 in Comparative Examples 2-5 and 2-6, R.sup.2 is arylamido; and in the molecular structure of compounds EMT-3 and EMT-4 in Comparative Examples 2-7 and 2-8, the arylamido on the naphthalene ring and naphthyl are not located in the orthortho position. Therefore, these compounds may not accord with the definition requirement of claim 1 and thus may not achieve the technical effect of the present invention.
[0418] It can be seen from the above results that the above compounds may be used as hole transport (HTL) materials, and also used as electron blocking layer (EBL) materials in combination with other hole-transport materials. When the above compounds are used as hole-transport materials, voltage of all the examples reduces significantly, and performance and service life are improved obviously. When the above compounds are in combination with other hole-transport materials for use, voltage of the device of all the examples increases slightly, and efficiency and service life of the device are further improved substantially. By the comparison between the molecular structure modeling (
Devices Utilizing the Compounds of Preferred Embodiment III
Example 3-1
[0419] This example provides an organic electroluminescent device, and the specific preparation process is as follows:
[0420] a glass pane coated with an ITO transparent conducting layer was subjected to ultrasonic treatment in a commercial detergent, washed in deionized water, and subjected to ultrasonic degreasing in a mixed solvent of acetone: ethanol, and baked in a dean environment till water was removed completely; then washed with UV-light and ozone, and the surface thereof was bombarded with a low-energy cationic beam;
[0421] the above glass substrate with an anode was put to a vacuum chamber, and vacuumized to be less than 1×10.sup.−5 Pa; the above anode coating film was evaporated with HI-3 under vacuum as a hole injection layer, where the evaporation rate was 0.1 nm/s and the evaporation coating thickness was 10 nm;
[0422] HT-4 was evaporated above the hole injection layer under vacuum as a hole transport layer of the device, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 60 nm;
[0423] the compound T1 was evaporated above the hole transport layer under vacuum as an electron blocking layer of the device, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 60 nm;
[0424] a luminescent layer of the device was evaporated above the electron blocking layer under vacuum; the luminescent layer includes a host material and a dyeing material; a multi-source co-evaporation method was used to adjust the evaporation rate of the host material GPH-59 to 0.1 nm/s; the evaporation rate of the dye RPD-8 was set by a ratio of 3%, and the total evaporation coating thickness was 40 nm;
[0425] an electron transport layer (material: ET-46) was evaporated above the luminescent layer under vacuum, and set by a ratio of 50%, and ET-57 was set by a ratio of 50%, where the evaporation rate was 0.1 nm/s and the total evaporation coating thickness was 25 nm;
[0426] LIF with a thickness of 0.5 nm, as an electron injection layer, was evaporated above the electron transport layer (ETL) under vacuum, and an Al layer with a thickness of 150 nm served as a cathode of the device.
Examples 3-2 to 3-25 and Comparative Example 3-1
[0427] The preparing process of Examples 3-2 to 3-12 and Comparative Example 3-1 is the same with that in Example 3-1, and the difference is that the compound T1 of the electron blocking layer material is replaced with the compounds as shown in Table 3.
[0428] The electron blocking layer material in Comparative Example 3-1 has the following structure (see details in patent WO2019/004587A1)
##STR00480##
[0429] Performance measurement is performed on the organic electroluminescent device prepared by the above process below:
[0430] at a same luminance value, a PR750 photoradiometer and an ST-86LA luminance meter (Beijing Normal University Photoelectric Instrument Plant) as well as a Keithley4200 test system were used to measure the driving voltage, current efficiency and service life of the organic electroluminescent device prepared in Examples and Comparative Examples. Specifically, voltage was increased at a rate of 0.1 V/s, when the luminance of the organic electroluminescent device was up to 5000 cd/m.sup.2, the voltage was measured as the driving voltage, and electric current density was measured at this time simultaneously; the ratio of the luminance to the electric current density was the current efficiency; LT95 life test was as follows: a luminance meter was used to keep a constant current under a luminance value of 5000 cd/m.sup.2; the time when the luminance of the organic electroluminescent device dropped to 4750 cd/m.sup.2 was measured with a unit of hour. The service life in Comparative Example 3-1 was set as a standard 100%, others were the ratios thereto. The measured results were shown in table 4.
TABLE-US-00004 TABLE 4 Electron blocking Desired Current LT95 layer luminance Voltage efficiency service material cd/m V cd/A life % Comparative C1 5000.00 5.5 13 100 Example 3-1 Examples 3-1 T1 5000.00 5.0 17.2 250 Examples 3-2 T2 5000.00 4.8 18.3 300 Examples 3-3 T11 5000.00 4.9 18.1 289 Examples 3-4 T12 5000.00 4.5 17.6 310 Examples 3-5 T81 5000.00 4.8 16.4 350 Examples 3-6 T163 5000.00 5.0 17.5 276 Examples 3-7 T170 5000.00 4.7 18.1 360 Examples 3-8 T232 5000.00 4.8 17.9 300 Examples 3-9 T54 5000.00 4.8 18.1 350 Examples 3-10 T237 5000.00 5.2 17.2 290 Examples 3-11 T248 5000.00 4.8 17.6 320 Examples 3-12 T255 5000.00 4.9 17.8 330
[0431] It can be seen from the results of Table 4 that when the compounds provided by the present invention are used as the electron blocking layer materials of the organic electroluminescent device, and when the luminance is up to 5000 cd/m.sup.2, the driving voltage is 4.5-5.2V, and the current efficiency is 16.4-18.3 cd/A. Therefore, the compounds of the present invention may effectively reduce the driving voltage, improve the current efficiency and prolong the service life of the device, and thus is a kind of electron blocking material with good performances.
[0432] In the electron blocking layer material C1 used in Comparative Example 1-1, the group substituted on the naphthalene ring is phenyl, and there is no binaphthyl group in the present invention. Therefore, the performance of the device in Comparative Example 1-1 decreases obviously relative to the examples, and the driving voltage is up to 5.5 V, while the current efficiency is only 13 cd/A.
[0433] Apparently, the above examples are merely used to specify the present invention clearly, but are not intended for limiting the embodiments. A person skilled in the art may make other changes or alterations in different forms based on the above description. All the embodiments need not be and may not be illustrated herein. Apparent changes or alterations derived thereby should fall within the protection scope of the present invention.