Heteroleptic iridium complexes as dopants

Abstract

To provide novel phosphorescent heteroleptic iridium complexes with phenylpyridine and dibenzo-containing ligands.SOLUTION: Novel phosphorescent heteroleptic iridium complexes with phenylpyridine and dibenzo-containing ligands are provided. Alkyl substitution at specific positions on the ligands gives rise to compounds with improved OLED properties, including saturated green emission.SELECTED DRAWING: Figure 3

Description

[Technical Field]

[0001] The claimed invention is based on one or more of the following collaborative university-industry research agreements: Organizations include: University of Michigan Board of Trustees, Princeton University, University of Southern California, and By Universal Display Corporation, by one or more parties, one The foregoing agreements are made for and / or in connection with one or more of the above entities. The invention claimed in the claims was in force on or before the date of the invention and the claims The invention described in was made as a result of activities carried out within the scope of said agreement.

[0002] The present invention provides heteroleptic iridium complexes suitable for incorporation into OLED devices. Regarding the body. [Background technology]

[0003] Optoelectronic devices that use organic materials are becoming increasingly desirable for a number of reasons. Many of the materials used to make such devices are are significantly cheaper, making organic optoelectronic devices more cost-effective than inorganic devices. In addition, the inherent properties of organic materials, e.g. Their flexibility makes them well suited for specific applications such as fabrication on flexible substrates. Examples of organic optoelectronic devices include organic light emitting devices (OLEDs). , organic phototransistors, organic photovoltaic cells, and organic photodetectors. Organic materials can have performance advantages over conventional materials. For example, organic light-emitting layers can emit light. The wavelength of light emitted can generally be easily tuned with appropriate dopants.

[0004] OLEDs are thin organic films (or polymers) that emit light when a voltage is applied across the device. OLEDs are widely used in flat panel displays, lighting, and backlighting. It is becoming an increasingly interesting technology for use in applications such as wire rope. The substance and composition of ED are as described in U.S. Patent Nos. 5,844,363 and 6,303,238. and 5,707,745, which are incorporated herein by reference in their entirety. The bodies are incorporated herein by reference.

[0005] One application of phosphorescent molecules is in full color displays. The industry standard for color filters is for pixels ( In particular, these standards require saturated red, green, and blue pixels. Color can be measured using CIE coordinates, which are well known in the art.

[0006] An example of a green emitting molecule is tris(2-phenylpyridine)iridine, denoted as Ir(ppy)3. and methylpropional, which has the structure of Formula I: [ka]

[0007] In this formula and in the figures later in this specification, the dative bond from nitrogen to the metal (here Ir) is a straight line. represent.

[0008] As used herein, the term "organic" refers to organic optoelectronic devices. This includes polymeric materials as well as small molecule organic materials that can be used to fabricate "Small molecule" means any organic substance that is not a polymer, and a "small molecule" is In fact, they may be very large. Small molecules may contain repeating units in some circumstances. For example, using a long-chain alkyl group as a substituent removes a molecule from the "small molecule" class. Small molecules can be used, for example, as pendant groups on the polymer backbone or as part of the backbone. The small molecule may be incorporated into the polymer as a series of small molecules built up on a core residue. They can also serve as the core residue of a dendrimer, which consists of a chemical shell. The residues can be fluorescent or phosphorescent small molecule emitters. Dendrimers are "small molecule" All dendrimers currently used in the field of OLEDs are small molecules. It is thought that there is.

[0009] As used herein, "top" means furthest from the substrate, while "bottom" means " means closest to the substrate. A first layer is described as "disposed over" a second layer. In this case, the first layer is positioned farther from the substrate. Unless otherwise specified, there may be another layer between the first and second layers. For example, the cathode is connected to the anode even though there are various organic layers between them. It can be described as "placed on top of."

[0010] As used herein, "solution processable" means a compound in the form of a solution or suspension. and / or This means that it can be deposited from

[0011] If a ligand is considered to directly contribute to the photoactive properties of the luminescent material, then the ligand is It is believed that the ligands do not contribute to the photoactive properties of the luminescent material. When a ligand is used, it can be said to be "ancillary," but the ancillary ligand does not have the characteristics of a photoactive ligand. Can change gender.

[0012] As used herein, and as commonly understood by those skilled in the art, a first " Highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO) energy level If its first energy level is closer to the vacuum energy level, then the second HO "Larger" or "higher" than the MO or LUMO. The ionization potential (IP) is It is measured as negative energy relative to the vacuum level, so it has a higher HOMO energy level. A higher rank corresponds to an IP with a smaller absolute value (a more negative IP). A lower LUMO energy level corresponds to an electron affinity (EA) with a smaller absolute value ( On a conventional energy level diagram with the vacuum level at the top, , the LUMO energy level of a material is higher than the HOMO energy level of that same material. A "higher" HOMO or LUMO energy level is higher than a "lower" HOMO or LUMO appears closer to the top of such a diagram than the O energy level.

[0013] As used herein, and as generally understood by those skilled in the art, a first work relationship The number is "" if the first work function has a higher absolute value than the second work function. "large" or "high." The work function is usually measured as a negative value relative to the vacuum level. So this means that a "higher" work function is more negative. On a conventional energy level diagram with a vacuum level at the top, a "higher" work function is The HOMO and LUMO energies are shown as The definition of the -level follows a different convention than the work function.

[0014] Further details regarding OLEDs and the above definitions can be found in U.S. Pat. No. 7,279,704. No. 6,293,494, the entire contents of which are incorporated herein by reference. [Prior art documents] [Patent documents]

[0015] [Patent Document 1] U.S. Patent No. 5,844,363 [Patent Document 2] U.S. Patent No. 6,303,238 [Patent Document 3] U.S. Patent No. 5,707,745 [Patent Document 4] U.S. Patent No. 7,279,704 [Non-patent literature]

[0016] [Non-Patent Document 1] Baldo et al., “Highly Efficient Phosphorescent Emission from Organic Electroluminescent Devices”, Nature, vol. 395, 151-154, 1998 [Non-patent document 2] Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence”, Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) Summary of the Invention [Means for solving the problem]

[0017] In one aspect, the compound of the formula: [ka] The present invention provides a compound having the formula: R1 and R2 may be optionally linked, and the number of carbon atoms in R1 and R2 The sum of R3, R4, R5, and R6 is at least 2. R3, R4, R5, and R6 are optionally linked together. is also good, and R a and R b represents mono-, di-, tri-, or tetra-substitution. X represents BR, NR , PR, O, S, Se, C=O, S=O, SO2, CRR′, SiRR′, and GeRR ', and R a , R b , R, R′, R1, R2, R3, R4, R R5 and R6 are independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroaromatic alkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, aryl nitrile, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfur selected from the group consisting of phenyl, sulfonyl, phosphino, and combinations thereof; and n is 1 or 2.

[0018] In one aspect, n is 2. In one aspect, X is O. In one aspect, R1 is In another aspect, R1 is alkyl and R2 is hydrogen. In one aspect, R1 and R2 are alkyl. In one aspect, R1 and R In another aspect, R1 and R2 are independently a branched alkyl , cyclic alkyl, bicycloalkyl, and polycyclic alkyl. In one aspect, R1 or R2 is isopropyl.

[0019] In one aspect, R1 and R2 contain one or more deuterium atoms. R4, R5, and R6 are independently hydrogen, deuterium, alkyl, aryl, and combinations thereof. In another aspect, any of R3, R4, R5, and R6 is selected from the group consisting of a combination thereof. At least one of the alkyl groups is a branched alkyl, a cyclic alkyl, a bicycloalkyl, or a polycyclic alkyl. In one aspect, R3, R4, R5, or R6 contains one or more deuterium atoms. nothing.

[0020] In one aspect, the compound is Compound 53, Compounds 157 to 159, Compound 165, Compound 174, Compound 175, Compounds 184 and 185, Compound 314, Compound 321, Compounds 625 to 628, Compound 633, Compound 643, Compounds 652 and 653, and Compounds 1145 and 1146 are selected from the group consisting of:

[0021] In one aspect, a first device is provided, the first device comprising a first organic light-emitting The device further includes an anode, a cathode, and a and the following formula: [ka] The organic layer comprises a compound having the formula: R1 and R2 may be optionally linked, and the number of carbon atoms in R1 and R2 The sum of R3, R4, R5, and R6 is at least 2. R3, R4, R5, and R6 are optionally linked together. is also good, and R a and R b represents mono-, di-, tri-, or tetra-substitution. X represents BR, NR , PR, O, S, Se, C=O, S=O, SO2, CRR′, SiRR′, and GeRR ', and R a , R b , R, R′, R1, R2, R3, R4, R R5 and R6 are independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroaromatic alkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, aryl nitrile, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfur selected from the group consisting of phenyl, sulfonyl, phosphino, and combinations thereof; and n is 1 or 2.

[0022] In one aspect, the first device is a consumer product. In another aspect, the first device comprises a lighting panel. In one aspect, the organic layer is an emissive layer and the compound is an emissive dopant. In this aspect, the organic layer is an emissive layer and the compound is a non-emissive dopant.

[0023] In one aspect, the organic layer further comprises a host. benzo-fused thiophenes or benzo-fused furans containing phenylene in the host Any of the substituents is C n H 2n+1 , O.C. n H 2n+1 , OAr1, N(C n H 2n +1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CHC n H 2n +1 , Ar1, Ar1-Ar2, C n H 2n -Ar1, substituted or unsubstituted, where Ar1 and Ar2 are independently benzene, biphenyl, from benzophenone, naphthalene, triphenylene, carbazole, and their heteroaromatic analogues and n is 1 to 10.

[0024] In one aspect, the host has the formula: [ka]

[0025] In another aspect, the host is selected from the group consisting of: [ka] and combinations thereof.

[0026] In one aspect, the host is a metal complex. [Brief explanation of the drawings]

[0027] [Figure 1] FIG. 1 shows an organic light-emitting device. [Figure 2] FIG. 2 shows an inverted organic light-emitting device that does not have a separate electron transport layer. [Figure 3] FIG. 3 shows the compound of formula I. DETAILED DESCRIPTION OF THE INVENTION

[0028] [Detailed explanation] Generally, an OLED is disposed between and electrically connected to an anode and a cathode. When a current is applied, the organic layer(s) are activated. The node injects holes, and the cathode injects electrons. The injected holes and electrons are then repelled. When the electron and hole are localized on the same molecule, the excited electron moves toward the oppositely charged electrode. An "exciton" is formed, which is a localized electron-hole pair with an energy state. Light is emitted when the exciton relaxes via a photoluminescent mechanism. Non-radiative mechanisms, e.g., thermal relaxation, can also occur. Although this is possible, it is generally considered undesirable.

[0029] Early OLEDs used emissive molecules that emitted light from their singlet state ("fluorescence"). For example, see U.S. Pat. No. 4,769,292, which is incorporated by reference in its entirety. Fluorescence emission generally occurs over a time frame of less than 10 nanoseconds. occurs in.

[0030] More recently, OLEDs have been demonstrated that have emissive materials that emit light from triplet states ("phosphorescence"). Baldo et al., "Highly Efficient Phosphorescent Emission from Organic Electrodes" 395, 151-154, 1998 (“Baldo-I”); and Baldo et al., “Very high-efficiency green organic light-emitting devices based on electrophosphorescence”, Appl. Phys. Lett., vol. 75, No. 3, 4-6 (1999) (“B aldo-II"), which are incorporated by reference in their entireties. Phosphorescence is disclosed in U.S. Pat. No. 7,279,700. This is described in more detail in columns 5-6 of the specification of No. 4, which is incorporated by reference.

[0031] FIG. 1 shows an organic light emitting device 100. This illustration is not necessarily drawn to scale. The device 100 includes a substrate 110, an anode 115, a hole injection layer 120, a hole transport layer 125, an electron transport layer 130, and a gate insulating layer 132. a blocking layer 130, an emitting layer 135, a hole blocking layer 140, an electron transport layer 145, an electron injection layer 150, a protective layer 155, and and a cathode 160. The cathode 160 has a first conductive layer 162 and a second conductive layer 164. The device 100 is fabricated by depositing the layers described, in order. The properties and functions of these various layers, as well as exemplary materials, are described in U.S. Pat. No. 5,704, columns 6-10, which are incorporated by reference. do.

[0032] More examples of each of these layers are available, e.g., flexible and transparent. Substrate-anode combinations are disclosed in U.S. Pat. No. 5,844,363. , which is incorporated by reference in its entirety. An example of a p-type doped hole transport layer is a 50:1 molar ratio of F4 -TCNQ doped m-MTDATA, which is US Patent Application Publication No. 2003 / 0039994. No. 0230980, the entire contents of which are incorporated by reference. Examples of emissive and host materials are described in U.S. Pat. No. 6,303,238 to Thompson et al. and is incorporated by reference in its entirety. An example of an n-type doped electron transport layer is a 1:1 BPhen doped with Li at a molar ratio of 0.1 to 0.2, which is disclosed in U.S. Patent Application Publication No. 2003 / 0029994. No. 0230980, the entire contents of which are incorporated by reference. U.S. Patent Nos. 5,703,436 and 5,707,745 (which (incorporated by reference in its entirety) uses a transparent, electrically conductive sputtered film overlaid thereon. A composite cathode having a thin layer of metal such as Mg:Ag with an ITO layer deposited thereon is then prepared. The theory and use of blocking layers is further described in U.S. Pat. No. 6,097,117. 47 and U.S. Patent Application Publication No. 2003 / 0230980. Examples of injection layers are found in U.S. Patent Application Publication No. 2004 / 0129994, which is incorporated by reference in its entirety. No. 04 / 0174116, the entire contents of which are incorporated by reference. The disclosure of which is found in U.S. Patent Application Publication No. 2004 / 0174116, the entire disclosure of which is incorporated herein by reference. Incorporated herein by reference.

[0033] Figure 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 212, and a cathode 214. The device 200 includes a light-emitting layer 215, a light-emitting layer 220, a hole-transporting layer 225, and an anode 230. The most common OLED configuration is the anode. The device 200 has a cathode disposed above it, and the device 200 has a cathode disposed below the anode 230. Because device 200 has a gate 215, it can be called an "inverted" OLED. Materials similar to those described for device 200 can be used for the corresponding layers of device 200. , provides one example of how some layers can be omitted from the structure of device 100. .

[0034] The simple layered structures illustrated in Figures 1 and 2 are provided as non-limiting examples; It will be appreciated that embodiments of the present invention can be used in connection with a variety of other structures. The specific materials and structures shown are exemplary in nature and other materials and structures may be used. Based on design, performance, and cost factors, practical OLEDs can be developed in a variety of ways. This can be achieved by combining the various layers described above, or by combining several layers. may be omitted entirely. Other layers not specifically described may also be included. Materials other than those specifically described may be used. Many of the examples described herein are not intended to be limiting. Although the various layers are described as comprising a material, combinations of materials (e.g., host and It is understood that mixtures of dopants, or more generally mixtures, may be used. Also, a layer may have various sublayers. The names used are not intended to be strictly limiting. For example, device 200 In the present embodiment, the hole transport layer 225 transports holes and injects holes into the light-emitting layer 220, so that the hole transport In one embodiment, the OLED comprises: It can be described as having an "organic layer" disposed between the cathode and the anode. The organic layer may comprise a single layer or may comprise various layers, for example, as described in connection with FIGS. The substrate may further include multiple layers of suitable organic materials.

[0035] Structures and materials not specifically described, such as those disclosed in U.S. Pat. No. 5,247,247, to Friend et al. 190, which is incorporated by reference in its entirety. As a further example, a single OLED (PLED) can also be used. OLEDs having organic layers of the following formula can be used. OLEDs are described, for example, in U.S. Pat. No. 6,239,493 to Forrest et al. As described in US Pat. No. 5,707,745, which is incorporated by reference in its entirety. The structure of an OLED can be a simple layered structure as shown in Figures 1 and 2. For example, the substrate may have a thickness of 1000 nm to improve light out-coupling. For example, U.S. Patent No. 6,091,195 to Forrest et al., which is incorporated by reference in its entirety. ) and / or U.S. Pat. No. 5,834,899 to Bulovic et al. No. 3, which is incorporated by reference in its entirety. The reflecting surface may include a

[0036] Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. For organic layers, preferred methods include thermal evaporation, Inkjet (e.g., U.S. Pat. No. 6,013,982 and U.S. Pat. No. 6,087 ,196 (which are incorporated by reference in their entireties), organic vapor phase synthesis Organic vapor phase deposition (OVPD) (see, e.g., U.S. Patent No. 6,444,445 to Forrest et al.) ,337,102 (incorporated by reference in its entirety), as well as Deposition by organic vapor jet printing (OVJP) See, for example, U.S. Patent Application Serial No. 10 / 233,470, which is incorporated by reference in its entirety. )). Other suitable deposition methods include spin coating and Other solution-based methods are also included. Solution-based methods are preferably performed using nitrogen or For other layers, preferred methods include thermal evaporation. Preferred patterning methods include deposition through a mask, cold welding (e.g. For example, U.S. Patent No. 6,294,398 and U.S. Patent No. 6,468,819 (which ), which is incorporated by reference in its entirety), and inkjet and O This includes patterning associated with some deposition methods such as VJD. Other methods are also used. The materials to be deposited can be modified to make them suitable for a particular deposition method. For example, branched or unbranched, preferably at least 3 carbon atoms Substituents such as alkyl and aryl groups containing Substituents having 20 or more carbons may be used, and 3 to 10 carbons may be used. 20 carbons is the preferred range. Materials with asymmetric structures tend to be more resistant than those with symmetric structures. Although they may have good solution processability, this is because asymmetric materials may have less tendency to recrystallize. Dendrimer substituents are used to enhance the ability of small molecules to undergo solution processing. You can be there.

[0037] Devices made in accordance with embodiments of the present invention can be incorporated into a variety of consumer products. These products include flat panel displays, computer monitors, televisions, and Notice boards, interior or exterior lighting and / or signal lights, head-up displays, Fully transparent displays, flexible displays, lasers Printers, telephones, mobile phones, personal digital assistants (PDAs), Laptop computers, digital cameras, camcorders, viewfinders, Displays, rides, large area walls, cinema or stadium screens Clean or labeled. Passive matrix and active matrix A variety of control mechanisms can be used to control devices fabricated in accordance with the present invention, including Most devices are stored at temperatures between 18°C ​​and 30°C, preferably room temperature (20-25°C). It is intended for use in a temperature range that is comfortable for humans.

[0038] The materials and structures described herein may have applications in devices other than OLEDs. For example, other optoelectronic devices, such as organic solar cells and organic photovoltaics. Detectors can use these materials and structures. More generally, organic devices, For example, organic transistors can use these materials and structures.

[0039] Halo, halogen, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, The terms alkyl, heterocyclic, aryl, aromatic, and heteroaryl are known in the art. and is defined in columns 31-32 of U.S. Pat. No. 7,279,704, is incorporated by reference.

[0040] In one embodiment, the compound has the formula: [ka] The present invention provides a compound having the formula: R1 and R2 may be optionally linked, and the number of carbon atoms in R1 and R2 The sum of is at least 2. Therefore, both R1 and R2 must have at least one represents a substituent having a carbon atom. If R1 does not represent a substituent containing carbon, R2 may be at least R3, R4 must represent a substituent containing at least two carbon atoms, and vice versa. , R5, R6 may be optionally linked, and R a and R b Mono, Ji, To X represents BR, NR, PR, O, S, Se, C=O, S=O, is selected from the group consisting of SO, CRR′, SiRR′, and GeRR′, and R a , R b , R, R', R1, R2, R3, R4, R5, and R6 are independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, Alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ester, Nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and and n is 1 or 2;

[0041] In one embodiment, n is 2. In one embodiment, X is O. In one embodiment, R1 is In another embodiment, R1 is alkyl and R2 is In one embodiment, R1 and R2 are hydrogen. In another embodiment, R1 and R2 are alkyl. R2 is independently selected from branched alkyl, cyclic alkyl, bicycloalkyl, and polycyclic alkyl. In one embodiment, R1 or R2 is isopropyl. Substitution at the 4- and 5-positions of either pyridine ring in the compound allows for the incorporation of When combined with other materials, they exhibit desirable properties such as saturated green emission, high efficiency, and long device lifetime. The photophysical properties of devices incorporating these compounds can be improved. The properties and device characteristics can be changed by changing the nature of the substituents at the 4- or 5-position of the pyridine. The 4-position on the pyridine ring in compounds of formula I is not occupied by an R5 or R1 substituent. The 5-position is the position occupied by an R4 or R2 substituent.

[0042] As used herein, the following structure: [ka] The fragment containing the DBX group, i.e., dibenzoX( d i b enzo X), where X is the Atoms A1 to A8 are any of the atoms or groups described in the specification. Atoms A1 to A8 are nitrogen or carbon. It can consist of:

[0043] In one embodiment, R1 and R2 contain one or more deuterium atoms. and R2 contains one or more deuterium atoms. In one embodiment, R3, R4, R5, and R6 are independently selected from the group consisting of hydrogen, deuterium, alkyl, aryl, and combinations thereof. In another embodiment, at least one of R3, R4, R5, and R6 is selected. It includes branched alkyl, cyclic alkyl, bicycloalkyl, or polycyclic alkyl. In the formula (I), R3, R4, R5, or R6 contains one or more deuterium atoms. Without being bound by theory However, the incorporation of deuterium results in a carbon-deuterium (CD) bond rather than a carbon-hydrogen (CH) bond. It is believed that the greater binding strength of the compound improves the stability of the compound. Therefore, compounds in which the unstable C—H bond is replaced by a C—D bond have a larger Without being bound by theory, the alkyl group of the ligand for the iridium complex is When deuterium atoms are incorporated into the group, the resulting complex has a longer device lifetime. It is thought that this is possible.

[0044] In one embodiment, the compound is selected from the group consisting of: [ka]

[0045] [ka]

[0046] [ka]

[0047] In one embodiment, suitable R1-R6 groups in compounds of Formula I include those having the substituent configurations in Table 1. Included.

[0048] [Table 1]

[0049] [Table 2]

[0050] [Table 3]

[0051]

Table 4

[0052]

Table 5

[0053]

Table 6

[0054]

Table 7

[0055]

Table 8

[0056]

Table 9

[0057]

Table 10

[0058]

Table 11

[0059]

Table 12

[0060]

Table 13

[0061]

Table 14

[0062]

Table 15

[0063] Table 16

[0064]

Table 17

[0065]

Table 18

[0066]

Table 19

[0067] Table 20

[0068] Table 21

[0069] Table 22

[0070] Table 23

[0071] Table 24

[0072] [Table 25]

[0073] [Table 26]

[0074] In one embodiment, a first device is provided. The first device comprises a first organic light-emitting device. The device further includes an anode, a cathode, and a , the following formula: [ka] The organic layer comprises a compound having the formula: R1 and R2 may be optionally linked, and the number of carbon atoms in R1 and R2 The sum of R3, R4, R5, and R6 is at least 2. R3, R4, R5, and R6 are optionally linked together. is also good, and R a and R b represents mono-, di-, tri-, or tetra-substitution. X represents BR, NR , PR, O, S, Se, C=O, S=O, SO2, CRR′, SiRR′, and GeRR ', and R a , R b , R, R′, R1, R2, R3, R4, R R5 and R6 are independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroaromatic alkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, aryl nitrile, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfur selected from the group consisting of phenyl, sulfonyl, phosphino, and combinations thereof; and n is 1 or 2.

[0075] In one embodiment, the first device is a consumer product. In another aspect, the first device comprises a lighting panel. In one embodiment, the organic layer is an emissive layer and the compound is an emissive dopant. In this embodiment, the organic layer is an emissive layer and the compound is a non-emissive dopant.

[0076] In one embodiment, the organic layer further comprises a host. In another embodiment, the host is a benzo-fused thiophenes or benzo-fused furans containing phenylene in the host Any of the substituents is C n H 2n+1 , O.C. n H 2n+1 , OAr1, N(C n H 2n +1 )2, N(Ar1)(Ar2), CH=CH-C n H 2n+1 , C≡CHC n H 2n +1 , Ar1, Ar1-Ar2, C n H 2n -Ar1, substituted or unsubstituted, where Ar1 and Ar2 are independently benzene, biphenyl, from benzophenone, naphthalene, triphenylene, carbazole, and their heteroaromatic analogues and n is 1 to 10.

[0077] In one embodiment, the host has the formula: [ka]

[0078] In another embodiment, the host is selected from the group consisting of: [ka] and combinations thereof.

[0079] In one embodiment, the host is a metal complex. [Example]

[0080] [Device example]

[0081] All device examples are manufactured in high vacuum (<10 -7 Fabricated by thermal evaporation (VTE) at 1000 Torr. The anode electrode was 1200 Å indium tin oxide (ITO). The cathode was All devices consisted of 10 Å of LiF followed by 1000 Å of Al. Immediately, the shield was sealed with epoxy resin in a nitrogen glove box (<1 ppm H2O and O2). The container was sealed with a sealed glass lid and a moisture absorbent was incorporated into the package.

[0082] The organic laminated layer of the device example consists of a hole injection layer (HIL) with a thickness of 100 Å, starting from the ITO surface. Compound C; 300 Å of 4,4′-bis[N-(1-naphthyl)-2-methyl-2-propanol] as a hole transport layer (HTL); as the light-emitting layer (EML); Compound D of the present invention doped with 15% by weight of the compound of formula I as a host. 300 Å of Compound D; 50 Å of Compound D as the blocking layer (BL); and 400 Å as the ETL. Compound A consisted of Alq (tris-8-hydroxyquinoline aluminum). A comparative device example using Compound B was prepared in the same manner as in the device example above. Compound A and Compound B were used as emitters in the EML.

[0083] The results of these devices and the data from these devices are summarized in Table 1. As used herein, NPD, Alq, Compound A, Compound B, Compound C, and Compound D are defined as follows: It has the following structure.

[0084] [ka]

[0085] [Table 27]

[0086] [Table 28]

[0087] Table 3 summarizes the device data: luminous efficiency (LE), external quantum efficiency (EQE), and power efficiency (PE) is measured at 1000 nits, while life (LT 80% )teeth , the device is 40mA / cm 2 At a constant current density of 1000, the brightness drops to 80% of its initial value. was defined as the time it took to lower

[0088] The advantages of alkyl substitution at the 4- and 5-positions of the DBX pyridine ring are evident from Table 3. Compared with Comparative Example 1, which does not have a substituent at the 4th or 5th position of the BX pyridine ring, the compound of Formula I is more It is more saturated (lower CIE x coordinate and shorter λ max ), measured at FWHM The breadth is comparable. In all of the compounds of the present invention, the voltage is lower and the LE The PE and EQE values ​​are all higher. Compounds 53, 158, 175, 633, and 6 In the case of 43, the PE is at least twice as high as in Comparative Example 1.

[0089] Comparative Example 2 (Compound B) having only one carbon atom (methyl) at the 4-position of the DBX pyridine ring ), compounds 53, 158, 174, 175, 184, 185, and 314 are C Compounds 157, 158, 159, and 165 have more saturated colors based on the x-coordinate of I.E. , 174, 175, 184, 185, 314, 321, and 626 all have shorter λ m ax Most of the compounds of Formula I have a narrower emission profile than Comparative Example 2. (measured by FWHM). Compounds 53, 158, 165, 314, 3 21, 625, 633, and 653 all have lower operating voltages than Comparative Example 2. Most of the compounds of Formula I have greater LE, PE, and EQE values ​​than Comparative Example 2. There are.

[0090] [Combination with other substances] The materials described herein as useful for a particular layer in an organic light emitting device may be used in conjunction with the It can be used in combination with a wide range of other substances present in the The emissive dopants disclosed herein are compatible with a wide range of host, transport, and blocking layers that may be present. It can be used in combination with blocking layers, injection layers, electrodes, and other layers. The substances mentioned above are not intended to be a limiting list of substances that may be useful in combination with the compounds described herein. These are non-limiting examples, and one of skill in the art should consult the literature to identify other materials that may be useful in combination. The references can be easily referenced.

[0091] [HIL / HTL]

[0092] The hole injection / transport substance used in the present invention is not particularly limited, and the compound is usually a hole injection / transport compound. Any compound can be used as long as it can be used as an inlet / transport substance. Examples of such substances include: These include, but are not limited to: Phthalocyanine or porphyrin derivatives; aromatic amine derivatives; indolocarbazole Derivatives; Polymers containing fluorohydrocarbons; Polymers with conductive dopants; Conductive polymers polymers, e.g., PEDOT / PSS; derivatives derived from compounds such as phosphonic acid and silane derivatives; Derived self-assembling monomers; metal oxide derivatives, e.g., MoO x ;p-type semiconductor organicization Compounds such as 1,4,5,8,9,12-hexaazatriphenylene hexacarbonite metal complexes, and crosslinkable compounds.

[0093] Examples of aromatic amine derivatives used in HIL or HTL include those with the following structures: but is not limited to these. [ka]

[0094] Ar 1 ~Ar 9 Each of the above is a compound selected from the group consisting of aromatic hydrocarbon ring compounds, e.g., benzene Biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenylene phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic The group consisting of cyclic compounds, such as dibenzothiophene, dibenzofuran, dibenzoseleno Phen, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, Carbazole, indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazo azole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidin pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole , benzimidazole, indazole, indoxazine, benzoxazole, benzoyl isoxazole, benzothiazole, quinoline, isoquinoline, cinnoline, quinazoline , quinoxaline, naphthyridine, phthalazine, pteridine, xanthene, acridine, phthalazine Phenazine, phenothiazine, phenoxazine, benzofuropyridine, furodipyridine, benzazine Thienobenzopyridines, thienodipyridines, benzoselenophenopyridines, and selenophenopyridines and a group selected from the aromatic hydrocarbon cyclic group and the aromatic heterocyclic group. The cyclic structure is composed of 2 to 10 cyclic structural units, which are the same or different groups selected from the group or at least one oxygen atom, nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom Atoms, chain structural units, and groups linked via an aliphatic cyclic group. Ar is hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aryl alkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkoxy Nyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl , carboxylic acids, esters, nitriles, isonitriles, sulfanyl, sulfinyl, sulfur and further a substituent selected from the group consisting of phenyl, phosphino, and combinations thereof. It has been replaced.

[0095] In one aspect, Ar 1 ~Ar 9are independently selected from the group consisting of: [ka]

[0096] k is an integer from 1 to 20; X 1 ~X 8 is C (including CH) or N; Ar 1 teeth It has the same groups as defined above.

[0097] Examples of metal complexes for use in HIL or HTL include, but are not limited to, those of the following general formula: Not limited. [ka]

[0098] M is a metal having an atomic weight greater than 40; (Y 1 -Y 2 ) is a bidentate ligand, Y 1 and Y 2 are independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer value between 1 and the maximum number of ligands that can be bound to the metal; m+n is the number of ligands that can be bound to the metal. is the maximum number of ligands that can be bound to

[0099] In one aspect, (Y 1 -Y 2 ) is a 2-phenylpyridine derivative.

[0100] In another aspect, (Y 1 -Y 2 ) is a carbene ligand.

[0101] In another aspect, M is selected from Ir, Pt, Os, and Zn.

[0102] In a further aspect, the metal complex is a metal complex having a structure similar to that of Fc in solution. + / Fc couple is about 0.6 It has a minimum oxidation potential of less than 5V.

[0103] 〔host〕

[0104] The light-emitting layer of the organic EL device of the present invention contains at least a metal complex as a light-emitting substance. is preferred, and may contain a host material using the metal complex as a dopant material. The host material is not particularly limited, and the triplet energy of the host is equal to that of the dopant. Any metal complex or organic compound can be used as long as the energy is greater than the

[0105] Examples of metal complexes used as hosts preferably have the following general formula: [ka]

[0106] M is a metal; (Y 3 -Y 4 ) is a bidentate ligand, and Y 3 and Y 4 are C, N independently , O, P, and S; L is an ancillary ligand; m is from 1 to 1000 mol% of the metal that can be bound to the metal; and m+n is the maximum number of ligands that can be bound to the metal. It's a large number.

[0107] In one aspect, the metal complex is [ka] is.

[0108] (ON) is a bidentate ligand, coordinating the metal to the O and N atoms.

[0109] In another aspect, M is selected from Ir and Pt.

[0110] In a further aspect, (Y 3 -Y 4 ) is a carbene ligand.

[0111] Examples of organic compounds used as hosts are selected from the group consisting of: aromatic Aromatic hydrocarbon cyclic compounds, such as benzene, biphenyl, triphenyl, triphenyl phenalene, phenanthrene, fluorene, pyrene, chlorine, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, the group consisting of aromatic heterocyclic compounds, for example, dibenzothiazolinone ... thiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran , benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridinium Dilindole, pyrrolodipyridine, pyrazole, imidazole, triazole, oxazole azole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole Azoles, pyridines, pyridazines, pyrimidines, pyrazines, triazines, oxazines, oxalates, Xathiazine, oxadiazine, indole, benzimidazole, indazole, indole Doxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline , isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine, Pteridines, xanthenes, acridines, phenazines, phenothiazines, phenoxazines, Benzofuropyridine, furodipyridine, benzothienopyridine, thienodipyridine, benzo di-selenophenopyridine and selenophenodipyridine; and the aromatic hydrocarbons described above. are the same or different groups selected from the cyclic group and the aromatic heterocyclic group; and oxygen atoms, nitrogen atoms, sulfur atoms, silicon atoms, phosphorus atoms, boron atoms, chain structural units, and two to four groups bonded to each other directly or via at least one of the aliphatic cyclic groups. A group of 10 cyclic structural units, where each group is hydrogen, deuterium, halide, alkyl, silyl, or chloroalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy, amino No, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl , heteroaryl, acyl, carbonyl, carboxylic acid, ester, nitrile, isonitri aryl, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinations thereof and further substituted with a substituent selected from the group consisting of:

[0112] In one aspect, the host compound contains at least one of the following groups in its molecule: : [ka]

[0113] R 1 ~R 7 are independently hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroaromatic alkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl , cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, aryl nitrile, carbonyl, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfur selected from the group consisting of phenyl, sulfonyl, phosphino, and combinations thereof; If it is aryl or heteroaryl, it has the same definition as Ar above. It has.

[0114] k is an integer from 0 to 20.

[0115] X 1 ~X8 is selected from C (including CH) or N.

[0116] [HBL]

[0117] A hole-blocking layer (HBL) is used to reduce the number of holes and / or excitons that leave the emissive layer. The presence of such a blocking layer in a device can be advantageously compared to a similar device without a blocking layer. Blocking layers can also provide substantially higher efficiencies than conventional devices. It can also be used to confine light emission to a desired region.

[0118] In one aspect, the compound used in the HBL is the same as that used as the host described above. Contains the same molecule.

[0119] In another aspect, the compound used in HBL has at least one of the following groups in its molecule: Includes one: [ka]

[0120] k is an integer from 0 to 20; L is an ancillary ligand; and m is an integer from 1 to 3.

[0121] [ETL]

[0122] The electron transport layer (ETL) can include a material capable of transporting electrons. The doping may be intrinsic (undoped) or doped. Examples of ETL materials are not particularly limited, and they can be used to enhance electrical conductivity. Any metal complex or organic compound may be used as long as it is normally used to transport the molecule. can.

[0123] In one aspect, the compound used for ETL has at least one of the following groups in its molecule: Also includes one. [ka]

[0124] R 1 is hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, aryl alkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkoxy alkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl nitrile, carboxylic acid, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfur and combinations thereof, which are selected from the group consisting of phenyl, ... It has the same definition as the Ar group.

[0125] Ar 1 ~Ar 3 has the same definition as the Ar group above.

[0126] k is an integer from 0 to 20.

[0127] X 1 ~X 8 is selected from C (including CH) or N.

[0128] In another aspect, metal complexes used in ETLs include those of the general formula: The present invention is not limited to these. [ka]

[0129] (ON) or (NN) is a bidentate ligand that coordinates the metal to the O,N or N,N atom. L is an ancillary ligand; m is a number between 1 and the maximum number of ligands that can be bound to the metal. It is an integer value.

[0130] In any of the above-mentioned compounds used in each layer of an OLED device, the hydrogen atoms can be partially or fully deuterated.

[0131] In addition to and / or in combination with the materials disclosed herein, many hole injectors materials, hole transport materials, host materials, dopant materials, exciton / hole blocking layer materials, electron transport and and electron injecting materials may be used in OLEDs. Non-limiting examples of substances that may be used in ED are listed below in Table 3. Table 3 is a non-limiting list of The following lists classes of substances, non-limiting examples of complexes for each class, and references disclosing the substances: It lists them.

[0132] [Table 29]

[0133] [Table 30]

[0134] [Table 31]

[0135] [Table 32]

[0136] [Table 33]

[0137] [Table 34]

[0138] Table 35

[0139] Table 36

[0140] Table 37

[0141] Table 38

[0142] Table 39

[0143] Table 40

[0144] Table 41

[0145] Table 42

[0146] Table 43

[0147] Table 44

[0148] [Table 45]

[0149] [Table 46]

[0150] [Table 47]

[0151] [Table 48]

[0152] [Table 49]

[0153] [Table 50]

[0154] [Table 51]

[0155] [Synthesis Example] Chemical abbreviations used throughout this specification are as follows: Cy is cyclohexyl; ba is dibenzylideneacetone, EtOAc is ethyl acetate, DME is dimethoxyethane, dppe is 1,2-bis(diphenylphosphino)ethane, THF is tetrahydrofuran , DCM is dichloromethane, S-Phos is dicyclohexyl (2′,6′-dimethoxy -[1,1′-biphenyl]-2-yl)phosphine.

[0156] [ka]

[0157] [Synthesis of 5-chloro-2-(dibenzo[b,d]furan-4-yl)pyridine] Dibenzo[b,d]furan-4-yl benzoate in dimethoxyethane (75 mL) and water (75 mL) Boronic acid (9.5 g, 44.8 mmol), 2,5-dichloropyridine (7.0 g, 47.0 mmol), Pd (PPh3)4 (2.6 g, 2.2 mmol) and potassium carbonate (18.6 g, 134 mmol) were added. The reaction mixture was degassed with nitrogen and then heated to reflux overnight. Water was added, the organic layer was separated, and the aqueous layer was extracted with 3 x 50 mL of dichloromethane and sodium sulfate. After removing the solvent under reduced pressure, the crude product was purified by dichloromethane. Chromatography on silica gel gave 11.7 g of crude product. The product was crystallized from hexane to give 9.5 g (76%) of 5-chloro-2-(dibenzo[b ,d]furan-4-yl)pyridine was obtained as white needles. Confirmed.

[0158] [ka]

[0159] [2-(dibenzo[b,d]furan-4-yl)-5-(1-propen-2-yl)pyridine Synthesis of gin 5-chloro-2-(dibenzo[b,d]furan-4-yl)pyridine (9.5 g, 34.0 mm ol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl (1.1 g, 2.7 mmol), and potassium phosphate tribasic monohydrate (23.5 g, 1 02 mmol) was added to toluene (200 mL) and water (20 mL), and the reaction mixture was degassed with nitrogen. Pd2(dba)3 (0.622 g, 0.679 mmol) and 4,4,5,5-tetramethyl 1-Propen-2-yl-1,3,2-dioxaborolane (7.7 mL, 40.8 m mol) was added and the reaction mixture was heated to reflux overnight. EtOAc and water were added and the The organic layers were separated and the aqueous layer was extracted with 3 x 50 mL of dichloromethane and dried over sodium sulfate. After removing the solvent under reduced pressure, 12.7 g of an amber oil was obtained. , chromatographed on silica using 9 / 1 (v / v) hexane / EtOAc Over the course of 1 hour, 7.5 g (77%) of 2-(dibenzo[b,d]furan-4-yl)-5-(1 (-propen-2-yl)pyridine was obtained as a white solid. This product was confirmed by GC / MS. and used without further purification.

[0160] [ka]

[0161] [Synthesis of 2-(dibenzo[b,d]furan-4-yl)-5-isopropylpyridine] 2-(dibenzo[b,d]furan-4-yl)-5-(1-propen-2-yl)pyridine In a hydrogenation bottle containing EtOH (150 mL), ethanol (7.5 g, 26.3 mmol) was added. The reaction mixture was degassed by bubbling nitrogen through it for 10 minutes. , 2.63 mmol) and Pt / C (0.26 g, 1.3 mmol) were added to the reaction mixture. The reaction mixture was placed in a Parr hydrogenator for 1 hour. The reaction mixture was filtered through a filtration tube and washed with dichloromethane to give 7.5 g (99%) of the desired product. The product was confirmed by GC / MS and NMR.

[0162] [ka]

[0163] [Synthesis of 5-chloro-2-(dibenzo[b,d]furan-4-yl)pyridine] Dibenzo[b,d]furan-4-yl in dimethoxyethane (200 mL) and water (200 mL) Boronic acid (25 g, 118 mmol), 2,4-dichloropyridine (19.2 g, 130 mmol), Pd (PPh3)4 (4.1 g, 3.5 mmol) and potassium carbonate (48.9 g, 354 mmol) were added. The reaction mixture was degassed with nitrogen and then heated to reflux overnight. Water was added, the organic layer was separated, and the aqueous layer was extracted with 3 x 50 mL of dichloromethane and sodium sulfate. After removing the solvent under reduced pressure, the crude product was purified by dichloromethane. Chromatography on silica gel gave 33.4 g of crude product. The product was crystallized from hexane to give 27.0 g (82%) of 4-chloro-2-(dibenzo[ (b,d)furan-4-yl)pyridine was obtained as white needles. and confirmed by NMR.

[0164] [ka]

[0165] [2-(dibenzo[b,d]furan-4-yl)-4-(1-propen-2-yl)pyridine Synthesis of gin 4-chloro-2-(dibenzo[b,d]furan-4-yl)pyridine (24.0 g, 86.0 m mol), dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2- (2.8 g, 6.9 mmol), and potassium phosphate tribasic monohydrate (59.3 g, 257 mmol) was added to toluene (400 mL) and water (40 mL), and the reaction mixture was degassed. Pd2(dba)3 (1.6 g, 1.7 mmol) and 4,4,5,5-tetramethyl-2- (1-propen-2-yl)-1,3,2-dioxaborolane (19.4 mL, 103 mmol) The reaction mixture was heated to reflux overnight. EtOAc and water were added and the organic layer was separated. The aqueous layer was separated and extracted with 3 x 50 mL of dichloromethane and dried over sodium sulfate. After removing the solvent under reduced pressure, 33.0 g of an amber oil was obtained. This crude product was purified by 9 / 1 Chromatography on silica using DCM / EtOAc (v / v) yielded 2 3.5 g (96%) of 2-(dibenzo[b,d]furan-4-yl)-4-(1-propenyl)- The product was confirmed by GC / MS and further purified as follows: This was used without further purification.

[0166] [ka]

[0167] [Synthesis of 2-(dibenzo[b,d]furan-4-yl)-4-isopropylpyridine] 2-(dibenzo[b,d]furan-4-yl)-4-(1-propen-2-yl)pyridine Dinol (8.0 g, 28 mmol) was added to a hydrogenation bottle containing EtOH (150 mL). The mixture was degassed by bubbling N for 10 min. Pd / C (0.60 g, To the reaction mixture was added Pt / C (0.55 g, 2.8 mmol). The mixture was placed in a Parr hydrogenator for 1 hour. The reaction mixture was filtered and washed with dichloromethane. The crude product was diluted with 9 / 1 (v / v) hemoglobin. Chromatography on silica gel using hexane / EtOAc gave 7.2 g ( 96%) of 2-(dibenzo[b,d]furan-4-yl)-4-isopropylpyridine The product was confirmed by GC / MS and NMR.

[0168] [ka]

[0169] [5-Bromo-2-(dibenzo[b,d]furan-4-yl)-4-methylpyridine ] A flask was charged with 2,5-dibromoethane (450 mL) and water (100 mL). 4-methylpyridine (30 g, 118 mmol), dibenzo[b,d]furan-4-ylboron Phosphoric acid (25 g, 118 mmol), Pd(PPh3)4 (1.4 g, 1.18 mmol), and K2CO3 ( The reaction mixture was heated to reflux for 15 hours. The mixture was allowed to drain and then cooled to room temperature. EtOAc and water were added, the organic layer was separated, and the aqueous layer The extract was extracted with 3 x 50 mL of dichloromethane and dried over sodium sulfate. After removal of the solvent, the crude product was chromatographed on silica gel using dichloromethane. This product was crystallized from hexane to give 29.7 g of crude product. 8.8 g (72%) of pure product was obtained, which was confirmed by NMR and HPLC (99.3%). % purity).

[0170] [ka]

[0171] [Synthesis of 2-(dibenzo[b,d]furan-4-yl)-4,5-dimethylpyridine] 5-Bromo-2-(dibenzo[b,d]furan-4-yl)-4-methylpyridine (28 0.7 g, 85 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl [2-(2-methyl-2-yl)phosphine (1.394 g, 3.39 mmol), and potassium phosphate monohydrate (58 0.6 g, 255 mmol) was added to toluene (500 mL) and water (50 mL) and degassed for 20 minutes. Trimethylboroxine (14.83 mL, 106 mmol) and Pd2(dba)3 (0.777 g, 0.8 49 mmol) was added and the reaction mixture was heated to reflux overnight. After cooling, the organic layer was separated. The aqueous layer was extracted with 3 x 50 mL of EtOAc, dried over sodium sulfate, and evaporated. This crude product was purified by eluting it with 8 / 2 (v / v) dichloromethane / EtOAc (in hexane). Chromatography on silica gel using 19.2 g of a gray solid was obtained. This was recrystallized from hexane to give 16.8 g (83%) of the product as white needles. The product was confirmed by NMR and HPLC (99.97% purity).

[0172] [ka]

[0173] [2-(dibenzo[b,d]furan-4-yl)-5-isobutyl-4-methylpyridine Synthesis of 5-Bromo-2-(dibenzo[b,d]furan-4-yl)-4-methylpyridine (13 0.0 g, 38.3 mmol), isobutylboronic acid (11.7 g, 115 mmol), dicyclohexyl (2 ′,6′-Dimethoxy-[1,1′-biphenyl]-2-yl)phosphine (0.63 g, 1. 53 mmol), and potassium phosphate monohydrate (22.1 g, 96 mmol) in water (10 mL) and toluene. The system was degassed with nitrogen for 20 minutes and then Pd2(dba)3( 0.35 g, 0.38 mmol) was added, and the system was then heated to reflux overnight. Afterwards, the reaction mixture was filtered through a small plug of silica gel and eluted with dichloromethane. The filtrate was concentrated and then crystallized from hexane to give 2-(dibenzo[b,d]furan- 4-yl)-5-isobutyl-4-methylpyridine (9.0 g, 74%) was obtained.

[0174] [ka]

[0175] [Synthesis of 5-chloro-2-phenylpyridine] 2,5-Dichloropyridine (30 g, 203 mmol), phenylboronic acid (24.72 g, 203 mmol), 1), and potassium carbonate (84 g, 608 mmol) in dimethoxyethane (500 mL) and water (100 The reaction mixture was degassed with nitrogen for 20 minutes and Pd(PPh3)4 (2.3 mL) was added. g, 2.0 mmol) was added and the reaction mixture was allowed to reflux for 18 hours. The reaction was cooled to room temperature. Remove the aqueous layer and dry the dichloromethane by rotary evaporating under reduced pressure. The residue was dissolved in DMC, passed through a pad of silica gel, and washed with DCM. The solvent was removed and the crude product was eluted in 40 / 60 (v / v) DCM / hexane for 5 min. Chromatography on silica using 0 / 50 (v / v) DCM / hexane This gave 28 g (73%) of the product as a white solid (HPLC purity: 99.7%).

[0176] [ka]

[0177] [Synthesis of 5-ethyl-2-phenylpyridine] 5-Chloro-2-phenylpyridine (16 g, 84 mmol) and Ni(dppe)Cl2 (0 The resulting solution (0.891 g, 1.687 mmol) was added to 300 mL of THF and the reaction mixture was heated under nitrogen for 20 min. The mixture was degassed for 1 minute and then cooled to 0°C. Ethyl magnesium bromide (169 mL, 169 (mmol) was added dropwise over 60 min and the reaction mixture was stirred for an additional 3 h, after which The reaction mixture was cooled back to 0°C and quenched with 250 mL of water. The crude material was extracted with EtOAc, the organic layer was dried over sodium sulfate and filtered. Chromatography on silica using 95 / 5 hexane / EtOAc gave 2 Obtained 0.9 g (19%) of 5-ethyl-2-phenylpyridine as a white solid.

[0178] [ka]

[0179] [Synthesis of 2-phenyl-5-(1-propen-2-yl)pyridine] In a 1 L round-bottom flask, 5-chloro-2-phenylpyridine (10.15 g, 53.5 mmol), Dicyclohexyl(2',6'-dimethoxy-[1,1'-biphenyl]-2-yl)phosphatase Sphingosine (1.8 g, 4.3 mmol), potassium phosphate tribasic monohydrate (37.0 g, 161 mmol) was added along with toluene (200 mL) and water (20 mL). The reaction mixture was heated under nitrogen for 20 minutes. The mixture was degassed with nitrogen. ,3,2-dioxaborolane (12.07 mL, 64.2 mmol) and Pd2(dba)3 (0.980 g , 1.070 mmol) was added and the reaction mixture was refluxed for 18 hours. The aqueous layer was removed and the organic layer was dried. The crude product was purified by silica gel chromatography using 0-20% EtOAc in hexanes. Column chromatography on the above gave 11 g of the desired product (HPLC purity). The product was confirmed by GC / MS.

[0180] [ka]

[0181] [Synthesis of 2-phenyl-5-isopropylpyridine] 2-Phenyl-5-(1-propen-2-yl)pyridine (11 g, 56.3 mmol) was added to E The reaction mixture was then added to a hydrogenation bottle containing 150 mL of HCl. The reaction mixture was then purged with N2 for 10 min. The mixture was degassed by rinsing. Pd / C (0.60 g, 5.63 mmol) and Pt / C (0 0.55 g, 2.82 mmol) was added to the reaction mixture. The reaction mixture was placed in a Parr hydrogenator. Allow to stand for 1.5 hours. Filter the reaction mixture through a tightly packed bed of Celite®. The solvent was removed by rotary evaporation and analyzed by GC / MS. Complete conversion was confirmed. The crude product was passed through Celite (registered trademark) for column chromatography. The crude product was adsorbed onto silica gel using 10% EtOAc in hexanes. Chromatography as above gave 6 g (54%) of 2-phenyl-5-isopropyl Pyridine (HPLC purity: 100%) was obtained. This product was confirmed by GC / MS.

[0182] [ka]

[0183] [Synthesis of 4-chloro-2-phenylpyridine] In a 1 L round-bottom flask, add 2,4-dichloropyridine (30 g, 203 mmol), phenylboron Acid (24.7 g, 203 mmol), potassium carbonate (84 g, 608 mmol), Pd(PPh3)4 (2.3 g, 2.0 mmol), dimethoxyethane (500 mL), and water (150 mL) were added to this mixture. The mixture was degassed and heated to reflux for 20 hours. After cooling, the aqueous layer was extracted with EtOAc. The fractions were combined and purified by column chromatography (SiO2, 5% EtOAc in hexanes to 34 g (88%) of 4-chloro-2-phenyl Pyridine was obtained and the product was confirmed by GC / MS and NMR.

[0184] [ka]

[0185] [Synthesis of 2-phenyl-4-(1-propen-2-yl)pyridine] 4-Chloro-2-phenylpyridine (14 g, 73.8 mmol) and potassium phosphate (51.0 g, The reaction mixture was heated under nitrogen for 20 minutes. Purged with nitrogen and then 4,4,5,5-tetramethyl-2-(1-propen-2-yl) -1,3,2-dioxaborolane (16.65 mL, 89 mmol), Pd2(dba)3 (1.35 g, To the reaction mixture was added S-Phos (2.42 g, 5.91 mmol) and HCl (1.48 mmol). The reaction mixture was refluxed for 18 h. After cooling, 100 mL of water was added, separated, and the aqueous layer was washed with 100 mL of ethyl acetate. The organic layer was passed through a silica gel plug and eluted with DCM. The solvent was evaporated. After allowing to stand, the crude product was purified by column chromatography (SiO2, 5% EtOAc in hexanes) to 10% EtOAc in hexanes) to obtain 13.5 g (90%) of 2-phenyl-4 -(1-propen-2-yl)pyridine was obtained.

[0186] [ka]

[0187] [Synthesis of 2-phenyl-4-isopropylpyridine] 2-phenyl-4-(1-propen-2-yl)pyridine (13.5 g, 69.1 mmol) The reaction mixture was added to a hydrogenation bottle containing EtOH (150 mL) and heated under N2 for 10 min. Degassing was performed by bubbling. Pd / C (0.736 g, 6.9 mmol) and Pt / C (0.674 g, 3.5 mmol) was added to the reaction mixture. The reaction mixture was subjected to Parr hydrogenation. The reaction mixture was filtered through a tightly packed bed of Celite®. The solvent was removed by rotary evaporation and analyzed by GC / MS. Complete conversion was confirmed. The crude product was adsorbed onto Celite for column chromatography. The crude product was chromatographed on silica gel using 10% EtOAc in hexane. Chromatography revealed that 10 g (75%) of 2-phenyl-4-isopropylpyridine (H The product was confirmed by GC / MS with a PLC purity of 99.8%.

[0188] [ka]

[0189] [Synthesis of 5-methyl-2-phenylpyridine] 2-Bromo-5-methylpyridine (30 g, 174 mmol), phenylboronic acid (25.5 g, 20 9 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-2 -yl)phosphine (2.86 g, 6.98 mmol), and potassium phosphate tribasic monohydrate (12 The reaction mixture was cooled to 100° C. for 2 hours (0.0 g, 523 mmol) and added to toluene (600 mL) and water (60 mL). The mixture was degassed with nitrogen for 20 minutes. Pd2(dba)3 (3.19 g, 3.49 mmol) was added, and The reaction mixture was refluxed for 18 hours. After cooling, the organic layer was separated and the aqueous layer was poured into 3 x 50 mL jars. The crude product was extracted with dichloromethane, dried over sodium sulfate and evaporated. Chromatography on silica gel using (v / v) hexane / EtOAc This was then distilled in a Kugelrohr apparatus (150°C, 100 mbar) to give 26 g (88%) of 5-methyl- The product was analyzed by NMR and GC / MS. HPLC purity: 99.2%.

[0190] [ka]

[0191] [Synthesis of 4-methyl-2-phenylpyridine] In a 1 L round-bottom flask, 2-chloro-4-methylpyridine (25 g, 196 mmol), phenyl Boronic acid (23.9 g, 196 mmol), potassium carbonate (81 g, 588 mmol), Pd(PPh3) 4 (2.3 g, 1.9 mmol), dimethoxyethane (500 mL), and water (150 mL) were added. The reaction mixture was degassed with nitrogen and heated to reflux for 22 hours. After cooling, the aqueous layer was The combined organic fractions were subjected to column chromatography (SiO2, Hexachlorobenzene). 28g (78%) from 5% EtOAc in hexane to 10% EtOAc in hexane The product was confirmed by NMR and GC / MS. I acknowledged it.

[0192] [ka]

[0193] [Synthesis of 4-ethyl-2-phenylpyridine] To 4-methyl-2-phenylpyridine (8 g, 47.3 mmol) in anhydrous THF (150 mL), At -78 °C, lithium diisopropylamide (LDA) (30.7 mL, 61.5 mmol) was added dropwise. The dark solution was stirred at −78° C. for 3 h, then CHCl (4.1 mL, 66.2 mmol) was added. ) was added dropwise. The reaction mixture was allowed to warm slowly to room temperature overnight. The sodium solution and EtOAc were added and the reaction was transferred to a separatory funnel. The layers were washed twice with EtOAc, and the combined organic layers were washed once with water. After removal of the solvent, the crude product The product was chromatographed on silica gel using 9 / 1 (v / v) hexane / EtOAc. After filtering, 5.5 g (63.5%) of 4-ethyl-2-phenylpyridine was obtained. HPLC purity: 99.0%.

[0194] [ka]

[0195] [Synthesis of chlorine-bridged dimer of 4-methyl-2-phenylpyridine] 4-Methyl-2-phenylpyridine (7 g, 41 mmol) and iridium(III) chloride hydrate (4.86 g, 13.79 mmol) with 2-ethoxyethanol (90 mL) and water (30 mL) The resulting reaction mixture was placed in a 500 mL round-bottom flask under a nitrogen atmosphere and heated to 130°C. The resulting precipitate was filtered and diluted with methanol (3-4 times) and hexane (3 times). The resulting product was dried to give 7.5 g (90%) of the desired product. This product was used without further purification.

[0196] [ka]

[0197] [Synthesis of 5-methyl-2-phenylpyridine chlorine-bridged dimer] 5-Methyl-2-phenylpyridine (12 g, 70.9 mmol) and iridium(III) chloride hydrate The product (7.1 g, 20.3 mmol) was dissolved in 2-ethoxyethanol (100 mL) and water (33.3 mL). The resulting reaction mixture was heated to 130°C. The resulting precipitate was filtered and diluted with methanol (3-4 times) and hexane ( The resulting product was dried to give 11.0 g (96%) of the desired product. This product was used without further purification.

[0198] [ka]

[0199] [Synthesis of 2-phenyl-5-isopropylpyridine chlorine-bridged dimer] 5-Isopropyl-2-phenylpyridine (6.0 g, 30.4 mmol) and iridium chloride (I II) hydrate (3.6 g, 10.1 mmol) was dissolved in 2-ethoxyethanol (100 mL) and water (33.3 mL The resulting reaction mixture was placed in a 500 mL round-bottom flask under a nitrogen atmosphere. The mixture was refluxed at 30°C for 18 hours. The resulting precipitate was filtered and washed with methanol (3-4 times) and hexane. The resulting product was dried and washed with water (3-4 times). The product was obtained and used without further purification.

[0200] [ka]

[0201] [Synthesis of 2-phenyl-4-isopropylpyridine chlorine-bridged dimer] 4-Isopropyl-2-phenylpyridine (8.0 g, 40.6 mmol) and iridium chloride (I II) The hydrate (7.4 g, 20.3 mmol) was dissolved in 2-ethoxyethanol (90 mL) and water (30 mL). The resulting reaction mixture was placed in a 500 mL round-bottom flask under a nitrogen atmosphere. The mixture was refluxed at 0°C for 18 hours. The resulting precipitate was filtered and washed with methanol (3-4 times) and hexane. The resulting product was dried to give 6.1 g (95%) of the desired product. The product was obtained and used without further purification.

[0202] [ka]

[0203] [Synthesis of 4-ethyl-2-phenylpyridine chlorine-bridged dimer] 4-Isopropyl-2-phenylpyridine (5.5 g, 30.0 mmol) and iridium chloride (I II) Hydrate (5.8 g, 16.5 mmol) in 2-ethoxyethanol (90 mL) and water (30 mL) The resulting reaction mixture was placed in a 500 mL round-bottom flask under a nitrogen atmosphere. The mixture was refluxed at 0°C for 18 hours. The resulting precipitate was filtered and washed with methanol (3-4 times) and hexane. The resulting product was dried to give 6.5 g (72%) of the desired product. The product was obtained and used without further purification.

[0204] [ka]

[0205] [Synthesis of 5-ethyl-2-phenylpyridine chlorine-bridged dimer] 5-Ethyl-2-phenylpyridine (2.9 g, 15.7 mmol) and iridium(III) chloride aqueous solution The solvate (1.8 g, 5.2 mmol) was dissolved in 2-ethoxyethanol (60 mL) and water (20 mL). The resulting reaction mixture was heated at 130°C in a 500 mL round-bottom flask under a nitrogen atmosphere. The resulting precipitate was filtered and diluted with methanol (3-4 times) and hexane (3 times). The resulting product was dried to give 2.45 g (89.3%) of the desired product. The product was obtained and used without further purification.

[0206] [ka]

[0207] [5-Methyl-2-phenylpyridine iridium trifluoromethanesulfonate ] The iridium dimer (11 g, 9.8 mmol) was suspended in 600 mL of dichloromethane. In a separate flask, silver(I) trifluoromethanesulfonate (5.3 g, 20.5 mmol) was added to Me Dissolve in OH (300 mL) and add to the dichloromethane solution at room temperature with continuous stirring. The reaction mixture was stirred overnight in the dark. Filtration through a bed of Celite® and removal of the solvent under reduced pressure gave 15 g (100%) of crude product. The product was obtained as a brownish-green solid and was used without further purification.

[0208] [ka]

[0209] [4-Methyl-2-phenylpyridine iridium trifluoromethanesulfonate ] The above iridium dimer (7.5 g, 6.6 mmol) was dissolved in 600 mL of dichloromethane. In a separate flask, silver(I) trifluoromethanesulfonate (3.5 g, 13.8 mmol) was added to Me Dissolve in OH (300 mL) and add to the dichloromethane solution at room temperature with continuous stirring. The reaction mixture was stirred overnight in the dark. Filtration through a bed of Celite® and removal of the solvent under reduced pressure gave 10 g (100%) of crude product. The product was obtained as a brownish-green solid and was used without further purification.

[0210] [ka]

[0211] [2-phenyl-5-isopropylpyridine iridium trifluoromethanesulfonate Salt synthesis The above iridium dimer (5.3 g, 4.3 mmol) was dissolved in 500 mL of dichloromethane. In a separate flask, silver(I) trifluoromethanesulfonate (2.3 g, 8.9 mmol) was dissolved in MeO Dissolve in 250 mL of HCl and add to the dichloromethane solution at room temperature with continuous stirring. The reaction mixture was stirred overnight in the dark. Filtration through a bed of Lite® and removal of the solvent under reduced pressure gave 6.9 g (100%) of crude product. The product was obtained as a brown solid and was used without further purification.

[0212] [ka]

[0213] [2-phenyl-4-isopropylpyridine iridium trifluoromethanesulfonate Salt synthesis The above iridium dimer (6.2 g, 4.94 mmol) was dissolved in 500 mL of dichloromethane. In a separate flask, silver(I) trifluoromethanesulfonate (2.7 g, 10.4 mmol) was added to Me Dissolve in OH (250 mL) and add to the dichloromethane solution at room temperature with continuous stirring. The reaction mixture was stirred overnight in the dark. Filtration through a bed of Celite® and removal of the solvent under reduced pressure gave 7.8 g (100%) of The product was obtained as a brownish-green solid and was used without further purification. .

[0214] [ka]

[0215] [4-Ethyl-2-phenylpyridine iridium trifluoromethanesulfonate ] The above iridium dimer (6.8 g, 5.7 mmol) was dissolved in 500 mL of dichloromethane. In a separate flask, silver(I) trifluoromethanesulfonate (3.2 g, 12.5 mmol) was added to Me Dissolve in OH (250 mL) and add to the dichloromethane solution at room temperature with continuous stirring. The reaction mixture was stirred overnight in the dark. Filtration through a bed of Celite® and removal of the solvent under reduced pressure gave 5.5 g (63%) of crude product. The product was obtained as a brownish-green solid and was used without further purification.

[0216] [ka]

[0217] [5-Ethyl-2-phenylpyridine Iridium Trifluoromethanesulfonate ] The iridium dimer (2.8 g, 2.4 mmol) was suspended in 500 mL of dichloromethane. In a separate flask, silver(I) trifluoromethanesulfonate (1.3 g, 4.91 mmol) was added to M Dissolve in 250 mL of eOH and add to the dichloromethane solution at room temperature with continuous stirring. The reaction mixture was stirred overnight in the dark. Filtration through a bed of Celite® and removal of the solvent under reduced pressure gave 3.6 g (100%) The product was obtained as a brownish-green solid, which was used without further purification. Ta.

[0218] [ka]

[0219] Synthesis of Compound 53 The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (3.5 g, 4.9 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-5-isopropylpyridine (3.5 g, 12.18 mmol) and 1,2-dihydroxybenzoyl-5-isopropylpyridine (3.5 g, 12.18 mmol) was added to the flask and inactivated for 20 hours. The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a silica gel pad and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The crude product was eluted using 1 / 1 (v / v) dichloromethane / hexane. Chromatography on silica gel using 53 gave 1.3 g (33%) of compound 53. Obtained as a yellow solid. The product was confirmed by HPLC (99.5% purity) and LC / MS. did.

[0220] [ka]

[0221] [Synthesis of Compound 157] The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (2.5 g, 3.50 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.5 g, 9.15 mmol) and 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.5 g, 9.15 mmol) was added to the inert The reaction mixture was refluxed under atmospheric pressure for 24 hours. The reaction mixture was cooled to room temperature and It was diluted with ethanol, Celite® was added, and the mixture was stirred for 10 minutes. The mixture was filtered over a small silica gel plug on a frit and diluted with ethanol (3-4 times). ) and hexane (3-4 times). The filtrate was discarded. The pad was then washed with dichloromethane to elute the product. The mixture was then removed to dryness, and the product was precipitated by adding isopropanol and dichloromethane under reduced pressure. The filtered material was washed with isopropanol and hexane and, by LC / MS, A mixture of fac- and mer-isomers was obtained. This mixture was dissolved in DMSO and The crude product was isomerized to the fac-isomer in 1 / 1 dichloromethane / Chromatography on silica gel with hexane yielded 1.4 g (52%) of Compound 157 was obtained as a yellow solid. This product was purified by HPLC (98.7% purity) and LC. Confirmed by MS.

[0222] [ka]

[0223] [Synthesis of Compound 158] The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (2.5 g, 3.37 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.5 g, 9.15 mmol) and 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.5 g, 9.15 mmol) was added to the inert The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a pad of silica gel and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The solvent was removed to half its volume and isopropanol was added. The product was precipitated by adding HCl and the dichloromethane was removed under reduced pressure. After washing with propanol and hexane and drying, 2.7 g (100%) of compound 158 was obtained as a yellow solid. The product was obtained as a colored solid. The purity was confirmed by HPLC (99.4% purity) and LC / MS. I acknowledged it.

[0224] [ka]

[0225] [Synthesis of Compound 159] The appropriate iridium trifluoromethane salt was dissolved in EtOH (30 mL) and MeOH (30 mL). Tanesulfonate complex (3.0 g, 4.04 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (3.0 g, 10.98 mmol) and 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (3.0 g, 10.98 mmol) was inactivated for 20 hours. The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a silica gel pad and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane The desired product had very low solubility. The crude product was eluted with 1 / 1 (v / v) dichloromethane / hexane. hexane, followed by column chromatography on silica gel with 4 / 1 dichloromethane / hexane. HPLC gave 0.3 g of the product as a yellow solid, which was purified by HPLC. (99.9% purity) and confirmed by LC / MS.

[0226] [ka]

[0227] Synthesis of Compound 165 The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (2.5 g, 3.25 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.5 g, 9.15 mmol) and 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.5 g, 9.15 mmol) was added to the inert The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a pad of silica gel and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The solvent was removed to half its volume and isopropanol was added. The product was precipitated by adding HCl and the dichloromethane was removed under reduced pressure. The crude product was washed with propanol and hexane and dried. Column chromatography on silica gel using fluoromethane / hexane was performed. 2 g (43%) of compound 165 was obtained as a yellow solid. This product was purified by HPLC (99.4%). % purity) and LC / MS.

[0228] [ka]

[0229] [Synthesis of Compound 174] The appropriate iridium trifluoromethane salt was dissolved in EtOH (50 mL) and MeOH (50 mL). Tanesulfonate complex (3.6 g, 4.68 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (3.6 g, 13.17 mmol) and 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (3.6 g, 13.17 mmol) was added to the flask and inactivated for 20 hours. The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a silica gel pad and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane The crude product was washed with 1 / 1 (v / v) dichloromethane / hexane to elute the product. 0.8 g of product was obtained by column chromatography on silica gel using The product was obtained as a solid. The product was confirmed by HPLC (98.6% purity) and LC / MS. did.

[0230] [ka]

[0231] Synthesis of Compound 175 The appropriate iridium trifluoromethane salt was dissolved in EtOH (30 mL) and MeOH (30 mL). Tanesulfonate complex (2.5 g, 3.25 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.66 g, 9.74 mmol) and 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.66 g, 9.74 mmol) was inactivated for 20 hours. The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a silica gel pad and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane The crude product was washed with 2 / 3 (v / v) THF / hexane to elute the product. Column chromatography on silica gel was carried out to obtain 0.8 g of product by HPLC. The product was obtained by slowly evaporating the DCM from a 1 / 3 DCM / hexane solution. This product was recrystallized by distillation to give 0.6 g (22%) as a yellow crystalline solid. The product was confirmed by HPLC (99.4% purity) and LC / MS.

[0232] [ka]

[0233] Synthesis of Compound 184 The appropriate iridium trifluoromethane salt was dissolved in EtOH (30 mL) and MeOH (30 mL). Tanesulfonate complex (3.0 g, 3.76 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (3.0 g, 10.98 mmol) and 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (3.0 g, 10.98 mmol) was inactivated for 20 hours. The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a silica gel pad and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane The crude product was washed with 1 / 1 (v / v) dichloromethane / hexane to elute the product. Column chromatography on silica gel using The product was obtained as a yellow solid. This product was purified by HPLC (99.8% purity) and LC / MS. So I confirmed it.

[0234] [ka]

[0235] Synthesis of Compound 185 The appropriate iridium trifluoromethane salt was dissolved in EtOH (30 mL) and MeOH (30 mL). Tanesulfonate complex (2.8 g, 3.51 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.88 g, 10.53 mmol) and 1,2-dihydroxybenzoyl-4,5-dimethylpyridine (2.88 g, 10.53 mmol) was heated under N2 The reaction mixture was cooled to room temperature, diluted with ethanol, and poured onto Celite®. The mixture was added and stirred for 10 minutes. The mixture was then poured onto a small pad of silica gel. The mixture was filtered and washed with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane to elute the product. The crude product was purified by silica gel chromatography using 2 / 3 (v / v) dichloromethane / hexane. Column chromatography as above gave 2.1 g (69%) of the product as a yellow solid. The product was confirmed by HPLC (99.9% purity) and LC / MS.

[0236] [ka]

[0237] Synthesis of Compound 314 The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (2.5 g, 3.37 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 2-methyl-4-methylpyridine (2.5 g, 7.93 mmol) and 2-methyl-4-methylpyridine (2.5 g, 7.93 mmol) was added at 20 The reaction mixture was cooled to room temperature, diluted with ethanol, and Wright® was added and the mixture was stirred for 10 minutes. Filter over a small silica gel pad and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The product was eluted by washing with methane. The solvent was removed to half its volume and isopropyl alcohol was added. Alcohol was added to precipitate the product, and the dichloromethane was removed under reduced pressure. The solid was washed with isopropanol and hexane and dried to give 3.0 g (100%) of the compound. 314 was obtained as a yellow solid. The product was purified by HPLC (99.6% purity) and LC / MS. I confirmed this.

[0238] [ka]

[0239] [Synthesis of Compound 321] The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (2.2 g, 2.86 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 2-methyl-4-methylpyridine (2.2 g, 6.98 mmol) and 2-methyl-4-methylpyridine (2.2 g, 6.98 mmol) was added at 20 The reaction mixture was cooled to room temperature, diluted with ethanol, and Wright® was added and the mixture was stirred for 10 minutes. Filter over a small silica gel pad and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The product was eluted by washing with methane. The solvent was removed to half its volume and isopropyl alcohol was added. Alcohol was added to precipitate the product, and the dichloromethane was removed under reduced pressure. The product was washed with isopropanol and hexane. The crude product was dissolved in 1 / 1 (v / v) dichloromethane. Column chromatography on silica gel using ethanol / hexane yielded 1.6 g ( The product was purified by HPLC (99.0% purity) and HPLC yield of compound 321 was 50% pure as a yellow solid. and confirmed by LC / MS.

[0240] [ka]

[0241] Synthesis of Compound 625 The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (2.2 g, 3.08 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4-isopropylpyridine (2.2 g, 7.66 mmol) and 1,2-dihydroxybenzoyl-4-isopropylpyridine (2.2 g, 7.66 mmol) was added to the inert The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a pad of silica gel and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The solvent was removed to half its volume and isopropanol was added. The product was precipitated by adding HCl and the dichloromethane was removed under reduced pressure. Wash with propanol and hexane to give 1.7 g (67%) of compound 625 as a yellow solid. The product was confirmed by HPLC (99.8% purity) and LC / MS.

[0242] [ka]

[0243] Synthesis of Compound 626 The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (2.5 g, 3.37 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4-isopropylpyridine (2.5 g, 8.70 mmol) and 1,2-dihydroxybenzoyl-4-isopropylpyridine (2.5 g, 8.70 mmol) was added to the inert The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a pad of silica gel and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The solvent was removed to half its volume and isopropanol was added. The product was precipitated by adding HCl and the dichloromethane was removed under reduced pressure. The crude product was washed with propanol and hexane and dried. Chromatography on silica gel using chloromethane / hexane gave 2.5 The product was purified by HPLC (99.4% purity). ) and LC / MS.

[0244] [ka]

[0245] [Synthesis of Compound 627] The appropriate iridium trifluoromethane salt was dissolved in EtOH (30 mL) and MeOH (30 mL). Tanesulfonate complex (3.0 g, 4.0 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4-isopropylpyridine (3.0 g, 10.4 mmol) was added to the inert The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a pad of silica gel and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The crude product was washed with 1 / 1 (v / v) dichloromethane / hexane to elute the product. Chromatography on silica gel using PEG-2000 yielded 2.0 g (60%) of the compound. Compound 627 was obtained as a yellow solid. The product was purified by HPLC (99.9% purity) and LC / MS. So I confirmed it.

[0246] [ka]

[0247] Synthesis of Compound 628 The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (3.0 g, 4.0 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4-isopropylpyridine (3.0 g, 10.5 mmol) and 1,2-dihydroxybenzoyl-4-isopropylpyridine (3.0 g, 10.5 mmol) was stirred for 24 hours under nitrogen atmosphere. The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. The mixture was filtered over a medium and washed with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane to remove the product. The crude product was eluted with 2 / 3 (v / v) dichloromethane / hexane. Chromatography on silica gel gave 2.1 g (64%) of the product as a yellow solid. The product was confirmed by HPLC (99.95% purity) and LC / MS.

[0248] [ka]

[0249] Synthesis of Compound 633 The appropriate iridium trifluoromethane salt was dissolved in EtOH (25 mL) and MeOH (25 mL). Tanesulfonate complex (2.5 g, 3.25 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4-isopropylpyridine (2.5 g, 8.70 mmol) and 1,2-dihydroxybenzoyl-4-isopropylpyridine (2.5 g, 8.70 mmol) was stirred for 20 hours under nitrogen atmosphere. The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a pad of gel and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The solvent was removed to half its volume and isopropanol was added. The product was precipitated by addition of dichloromethane and the dichloromethane was removed under reduced pressure. The crude product was washed with isopropyl alcohol and hexane and then dried. Chromatography on silica gel using chloromethane / hexane yielded 1.6 g (59%) of compound 633 was obtained as a yellow solid. The product was purified by HPLC (99.7% purity). and confirmed by LC / MS.

[0250] [ka]

[0251] [Synthesis of Compound 643] The appropriate iridium trifluoromethane salt was dissolved in EtOH (30 mL) and MeOH (30 mL). Tanesulfonate complex (2.4 g, 3.12 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4-ethylpyridine (2.69 g, 9.35 mmol) and 1,2-dihydroxybenzoyl-4-ethylpyridine (2.69 g, 9.35 mmol) was added to the flask under nitrogen atmosphere for 20 hours. The reaction mixture was cooled to room temperature, diluted with ethanol, and poured onto Celite®. The mixture was added and stirred for 10 minutes. The mixture was then poured onto a small pad of silica gel. The mixture was filtered and washed with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane to elute the product. The crude product was purified by silica gel chromatography using 2 / 3 (v / v) dichloromethane / hexane. Chromatography on a column gave 1.3 g (50%) of the product as a yellow solid. The product was confirmed by HPLC (100% purity) and LC / MS.

[0252] [ka]

[0253] Synthesis of Compound 652 The appropriate iridium trifluoromethane salt was dissolved in EtOH (30 mL) and MeOH (30 mL). Tanesulfonate complex (3.1 g, 3.9 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-dihydroxybenzoyl-4-isopropylpyridine (3.1 g, 10.9 mmol) and 1,2-dihydroxybenzoyl-4-isopropylpyridine (3.1 g, 10.9 mmol) was added to the inert The reaction mixture was cooled to room temperature, diluted with ethanol, and The mixture was stirred for 10 minutes. Filter on a pad of silica gel and wash with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The Celite® / silica plug was then washed with dichloromethane. The crude product was washed with 1 / 1 (v / v) dichloromethane / hexane to elute the product. Chromatography on silica gel using PEG-400 yielded 2.1 g (62%) of the compound. Compound 652 was obtained as a yellow solid. The product was purified by HPLC (99.9% purity) and LC / MS. So I confirmed it.

[0254] [ka]

[0255] [Synthesis of Compound 653] Iridium trifluoromethanesulfonate in EtOH (30 mL) and MeOH (30 mL) The carboxylate complex (2.4 g, 3.01 mmol) and 2-(dibenzo[b,d]furan-4-yl)-4- A mixture of isopropylpyridine (3.0 g, 9.02 mmol) was refluxed under nitrogen atmosphere for 20 hours. The reaction mixture was cooled to room temperature, diluted with ethanol, and Celite® was added. The mixture was stirred for 10 minutes. The mixture was filtered over a small pad of silica gel. The cells were washed with ethanol (3-4 times) and hexane (3-4 times). The filtrate was discarded. The silica / silica plug was then washed with dichloromethane to elute the product. The crude product was purified by silica gel chromatography using 2 / 3 (v / v) dichloromethane / hexane. Chromatography gave 0.96 g (45%) of the product as a yellow solid. The product was confirmed by HPLC (99.8% purity) and LC / MS.

[0256] [ka]

[0257] Synthesis of 2-(dibenzo[b,d]furan-4-yl)-4-ethyl-d3-pyridine 2-(dibenzo[b,d]furan-4-yl)-4-methyl in anhydrous THF (250 mL) Pyridine (15.3 g, 59.0 mmol) was added to lithium diisopropylamide (35.4 mL) at -78 °C. The dark solution was stirred at -78 °C for 2 h, then CD 3I (4.41 mL, 70.8 mmol) was added dropwise. The reaction mixture was allowed to warm slowly to room temperature overnight. Ammonium chloride solution and EtOAc were added and the reaction was transferred to a separatory funnel. The layers were separated, the aqueous layer was washed twice with EtOAc, and the combined organic layers were washed once with water. After removal of the solvent, the crude product was diluted with 8 / 2 (v / v) hexane / EtOAc, then 7 / 3 hexane / EtOAc. Chromatography on silica gel using hexane / EtOAc gave 14.5 g The product was obtained as a pale yellow solid. Recrystallization from hexane gave 12.9 g (79%) of 2 -(dibenzo[b,d]furan-4-yl)-4-ethyl-d3-pyridine was obtained. LC purity: 99.4%.

[0258] [ka]

[0259] [2-(dibenzo[b,d]furan-4-yl)-4-isopropyl-d6-pyridine Synthesis] 2-(dibenzo[b,d]furan-4-yl)-4-ethyl in anhydrous THF (100 mL) The d3-pyridine was dissolved and cooled to -78°C. Lithium diisopropylamide (19.0 CDI (mL, 38.0 mmol) was added dropwise and the reaction mixture was stirred at -78°C for 2 hours. was added dropwise and the reaction mixture was allowed to warm slowly to room temperature overnight. H, quenched with NH4Cl (aq.), EtOAc was added, and the biphasic mixture was separated by a separatory funnel. The layers were separated, the aqueous layer was washed twice with EtOAc, and the combined organic layers were washed with water. After removal of the solvent, the crude product was purified by silica gel chromatography using 8 / 2 (v / v) hexane / EtOAc. Chromatography on silica gel gave 6.4 g (86%) of 2-(dibenzo[b, d]furan-4-yl)-4-isopropyl-d6-pyridine was obtained. HPLC purity: 9 9.2%.

[0260] [ka]

[0261] [Synthesis of Compound 1145] The appropriate iridium trifluoromethane salt was dissolved in EtOH (30 mL) and MeOH (30 mL). Tanesulfonate complex (3.5 g, 4.9 mmol) and 2-(dibenzo[b,d]furan-4- A mixture of 1,2-diethylpyridine (3.5 g, 12.7 mmol) and 1,2-diethylpyridine (3.5 g, 12.7 mmol) was added to the inert The reaction mixture was cooled to room temperature, diluted with ethanol, and added with Celite. The mixture was then mixed with a small silica gel pack on a frit and stirred for 10 minutes. The mixture was filtered over a filter and washed with ethanol (3-4 times) and hexane (3-4 times). The Celite® / silica plug was then washed with dichloromethane to remove the product. The crude product was chromatographed on silica gel using dichloromethane. The product was purified by filtration to give 1.8 g (47%) of compound 1145 as a yellow solid. It was confirmed by HPLC (98.7% purity) and LC / MS.

[0262] [ka]

[0263] [Synthesis of Compound 1146] 2-(dibenzo[b,d]furan-4- (yl)-4-isopropyl-d6-pyridine and the appropriate iridium trifluoromethyl group The reaction mixture was mixed with the benzophenone sulfonate complex and heated to reflux for 16 hours. The mixture was diluted with ethanol, celite was added, and the mixture was stirred for 10 minutes. The material was filtered over a small silica gel plug on a frit and washed with ethanol (3-4 times) and The Celite® / silica packing was washed with hexane (3-4 times). The filtrate was discarded. The product was then washed with dichloromethane to dissolve the product. The crude product was dissolved in hexane for 50 min. Chromatography on silica gel with 70% dichloromethane gave 1.7 The product was purified by HPLC (99.5% purity) to give 1146 (43%) as a yellow solid. The results were confirmed by HPLC and LC / MS.

[0264] The various embodiments described herein are for illustrative purposes only and are not intended to limit the scope of the present invention. It is understood that many of the materials and structures described herein are not necessarily depicted. Other materials and structures may be substituted without departing from the spirit of the invention. The claimed invention therefore relates to the specific examples and preferred embodiments described herein. The present invention may include variations from the above embodiments, which will be apparent to those skilled in the art. It is understood that the various theories as to why this occurs are not intended to be limiting.

Claims

1. 1. A phosphorescent emitter for an organic light emitting device, comprising a heteroleptic iridium complex having the formula: 【Chemical 1】 (In the formula, R ａ or R ｂ The dashed line coming out of the R ａ or R ｂ and the benzene ring to which R is bonded. ａ or R ｂ means a single bond between R １ and R ２ are each independently selected from the group consisting of hydrogen, deuterium, alkyl of 1 to 4 carbon atoms, and combinations thereof; R １ and R ２ the total number of carbon atoms in is at least 2; X is selected from the group consisting of O, S, and Se; R ａ , R ｂ , R ３ , and R ６ are each independently selected from the group consisting of hydrogen, deuterium, alkyl, and combinations thereof; R 4 and R 5 are each independently selected from the group consisting of hydrogen, deuterium, alkyl of 1 to 2 carbon atoms, and combinations thereof; R a and R b represent mono-, di-, tri-, or tetra-substitutions; and n is 1 or 2. A phosphorescent emitter comprising:

2. 10. The phosphorescent emitter of claim 1, wherein the heteroleptic iridium complex has at least one of the following characteristics: In formula I, n is 2; In Formula I, X is O; In Formula I, R １ is hydrogen and R ２ is alkyl; In Formula I, R １ is alkyl, and R ２ is hydrogen; In Formula I, R １ and R ２ is alkyl; In Formula I, R １ or R ２ are independently selected from the group consisting of branched alkyl; In Formula I, R １ or R ２ is isopropyl; In Formula I, R １ or R ２ contains one or more deuterium atoms; In Formula I, R １ and R ２ contains one or more deuterium atoms; and In Formula I, R ３ , R ４ , R ５ , or R ６ contains one or more deuterium atoms.

3. 2. The phosphorescent emitter of claim 1, wherein n is 2 in formula I.

4. 2. The phosphorescent emitter of claim 1, wherein X is O in formula I.

5. In Formula I, R １ and R ２ 2. The phosphorescent emitter of claim 1, wherein is alkyl having 1 to 4 carbon atoms.

6. In Formula I, R １ and R ２ 10. The phosphorescent emitter of claim 1, wherein:

7. In Formula I, R １ or R ２ The phosphorescent emitter of claim 1 , wherein

8. In Formula I, R １ and R ２ The phosphorescent emitter of claim 1 , wherein

9. The heteroleptic iridium complex of formula I is as follows: 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 2. The phosphorescent emitter of claim 1, selected from the group consisting of:

10. 10. A consumer product comprising an organic light emitting device, the organic light emitting device comprising the phosphorescent emitter of any one of claims 1 to 9, and the consumer product is selected from the group consisting of a flat panel display, a computer monitor, a television, a billboard, an indoor or outdoor lighting and / or signal light, a heads-up display, a fully transparent display, a flexible display, a laser printer, a telephone, a mobile phone, a personal digital assistant (PDA), a laptop computer, a digital camera, a camcorder, a viewfinder, a microdisplay, a vehicle, a large area wall, a cinema or stadium screen, or a sign.

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