Patent Application
20230078029
This application claims priority to and the benefit of Korean Patent Application No. 10-2021-0012067, filed on Jan. 28, 2021, in the Korean Intellectual Property Office, the entire content of which is hereby incorporated by reference.
One or more aspects of embodiments of the present disclosure relate to a luminescence device and an amine compound for a luminescence device.
Recently, luminescence displays are being activity developed as image displays. A luminescence display is different from a liquid crystal display, and is so-called a self-luminescent display, in which holes and electrons injected from a first electrode and a second electrode recombine in an emission layer so that a light-emitting material including in the emission layer emits light to achieve display.
In the application of a luminescence device to a display, a decreased driving voltage, increased emission efficiency, and increased life span of the luminescence device are desired, and continuous development of materials for a luminescence device capable of stably achieving the requirements is desired.
One or more aspects of embodiments of the present disclosure are directed toward a luminescence device and an amine compound for a luminescence device, and for example, a luminescence device having high efficiency and an amine compound included in a hole transport region of a luminescence device.
One or more embodiments of the present disclosure provide an amine compound represented by Formula 1:
In Formula 1, R1 is represented by Formula 2-1, and R2 and R3 are each independently represented by Formula 2-2 or Formula 2-3.
In Formula 2-1, X may be O or S, Ra to Rd may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where any one among (e.g., one selected from among) Ra to Rd may be a site bonded to nitrogen of Formula 1, any one among Re to Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder are each independently a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded, and when Rd is bonded to the nitrogen of Formula 1, Re may be a hydrogen atom or a deuterium atom, or combined with adjacent Rf to form a ring.
*-(L1)m-Ar1. Formula 2-2
In Formula 2-2, L1 may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, Ar1 may be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, where a fluorenyl group is excluded, “m” may be an integer of 0 to 3, and when R2 and R3 in Formula 1 are both represented by Formula 2-2 at the same time (e.g., simultaneously), Ar1 is not a 1-naphthyl group.
In Formula 2-3, Y may be O or S, L2 may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, R4 may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring, R5 may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring, “n” and “p” may each independently be an integer of 0 to 3, “q” may be an integer of 0 to 4, where Formula 2-1 and Formula 2-3 are not the same (e.g., are different groups), when Ra of Formula 2-1 is bonded to the nitrogen of Formula 1, and Rh is an alkyl group or an aryl group, at least one selected from among R2 and R3 of Formula 1 is represented by Formula 2-3, when X of Formula 2-1 is S, Formula 2-3 is not a 4-dibenzothiophenyl group, and the amine compound represented by Formula 1 includes a compound in which optional hydrogen in a molecule is substituted with deuterium (e.g., at least one hydrogen in the amine compound represented by Formula 1 is optionally substituted with deuterium).
In an embodiment, R1 of Formula 1 may be represented by Formula 2-1-1, R2 of Formula 1 may be represented by Formula 2-3, and R3 of Formula 1 may be represented by Formula 2-2 or Formula 2-3.
In Formula 2-1-1, X may be O or S, Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and Rb to Rg may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring.
In an embodiment, R1 of Formula 1 may be represented by Formula 2-1-2, R2 of Formula 1 may be represented by Formula 2-2, and R3 of Formula 1 may be represented by Formula 2-2 or Formula 2-3.
In Formula 2-1-2, X may be O or S, Ri may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rg group to form a ring, Rb to Rd may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, and any one selected from among Re to Rg may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded.
In an embodiment, R1 of Formula 1 may be represented by Formula 2-1-2, R2 of Formula 1 may be represented by Formula 2-3, and R3 of Formula 1 may be represented by Formula 2-2 or Formula 2-3.
In Formula 2-1-2, X may be O or S, Ri may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rg group to form a ring, Rb to Rd may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, and any one selected from among Re to Rg may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded.
In an embodiment, R1 of Formula 1 may be represented by Formula 2-1-3, and R2 and R3 of Formula 1 may each independently be represented by Formula 2-2 or Formula 2-3.
In Formula 2-1-3, X may be O or S, Re may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rf group to form a ring, Ra to Re may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, and any one selected from among Rf to Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded.
In an embodiment, Formula 1 may be represented by Formula 3-1 or Formula 3-2.
In Formula 3-1 and Formula 3-2, Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, Rb to Rg may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, Y′ may be O or S, L2′ may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, R4′ may be a hydrogen atom, a deuterium atom, a halogen atom, or a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, and/or combined with an adjacent group to form a ring, R5′ may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring, n′ and p′ may each independently be an integer of 0 to 3, q′ may be an integer of 0 to 4, and X, Ar1, Y, L1, L2, R4, R5, “m”, “n”, “p” and “q” may each independently be the same as defined in Formula 2-1 to Formula 2-3.
In an embodiment, Formula 1 may be represented by any one selected from among Formula 4-1 to Formula 4-3.
In Formula 4-1 to Formula 4-3, Ri may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rg group to form a ring, Rb to Rd may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, any one selected from among Re to Rg may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded, L1′ and L2′ may each independently be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, R4′ may be a hydrogen atom, a deuterium atom, a halogen atom, or a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, and/or combined with an adjacent group to form a ring, R5′ may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring, n′ and p′ may each independently be an integer of 0 to 3, q′ may be an integer of 0 to 4, and Ar1 and Ar1′ may each independently be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, where a fluorenyl group is excluded, m′ may be an integer of 0 to 3, and X, Y, L1, L2, R4, R5, “m”, “n”, “p” and “q” may each independently be the same as defined in Formula 2-1 to Formula 2-3, where Ar1 and Ar1′ in Formula 4-1 are not 1-naphthyl groups at the same time (e.g., simultaneously).
In an embodiment, Formula 1 may be represented by any one selected from among Formula 5-1 to Formula 5-3.
In Formula 5-1 to Formula 5-3, Re may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rf group to form a ring, Ra to Re may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, any one selected from among Rf to Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder are each independently a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded, L1′ may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, Ar1 and Ar1′ may each independently be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, where a fluorenyl group is excluded, m′ may be an integer of 0 to 3, Y′ may be O or S, L2′ may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, R4′ may be a hydrogen atom, a deuterium atom, a halogen atom, or a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, and/or combined with an adjacent group to form a ring, R5′ may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring, n′ and p′ may each independently be an integer of 0 to 3, q′ may be an integer of 0 to 4, and X, Y, L1, L2, R4, R5, “m”, “n”, “p” and “q” may each independently be the same as defined in Formula 2-1 to Formula 2-3, where Ar1 and Ar1′ in Formula 5-1 are not 1-naphthyl groups at the same time (e.g., simultaneously).
In an embodiment, L1 and L2 of Formula 2-2 and Formula 2-3 may each independently be a direct linkage, a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent biphenyl group, or a substituted or unsubstituted naphthylenyl group.
In an embodiment, the amine compound represented by Formula 1 may be any one selected from among compounds represented in Compound Group 1 to Compound Group 3.
One or more embodiments of the present disclosure provide a luminescence device including a first electrode, a hole transport region provided on the first electrode, an emission layer provided on the hole transport region, an electron transport region provided on the emission layer, and a second electrode provided on the electron transport region, wherein the hole transport region includes an amine compound according to an embodiment.
In an embodiment, the hole transport region may include a hole injection layer disposed on the first electrode, and a hole transport layer disposed on the hole injection layer, and the hole transport layer or the hole injection layer may include the amine compound of an embodiment.
In an embodiment, the hole transport region may include a hole transport layer disposed on the first electrode, and an electron blocking layer disposed on the hole transport layer, and the electron blocking layer may include the amine compound of an embodiment.
The accompanying drawings are included to provide a further understanding of the present disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the present disclosure and, together with the description, serve to explain principles of the present disclosure. In the drawings:
The present disclosure may have one or more suitable modifications and may be embodied in different forms, and embodiments will be explained in more detail with reference to the accompanying drawings. The present disclosure may, however, be embodied in different forms and should not be construed as being limited to the embodiments set forth herein. Rather, all modifications, equivalents, and substituents that are included in the spirit and technical scope of the present disclosure should be included in the present disclosure.
Like reference numerals refer to like elements throughout, and duplicative descriptions thereof may not be provided. In the drawings, the dimensions of structures may be exaggerated for clarity of illustration. It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another element. Thus, a first element could be alternatively termed a second element without departing from the teachings of the present disclosure. Similarly, a second element could be alternatively termed a first element. As used herein, singular forms such as “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In the description, it will be further understood that the terms “includes,” “including,” “comprises,” and/or “comprising,” when used in this specification, specify the presence of stated features, numerals, steps, operations, elements, parts, or the combination thereof, but do not preclude the presence or addition of one or more other features, numerals, steps, operations, elements, parts, or the combination thereof.
In the description, when a layer, a film, a region, a plate, etc. is referred to as being “on” or “above” another part, it can be “directly on” the other part, or intervening layers may also be present. In contrast, when a layer, a film, a region, a plate, etc. is referred to as being “under” or “below” another part, it can be “directly under” the other part, or intervening layers may also be present. Also, when an element is referred to as being disposed “on” another element, it can be disposed under the other element.
As used herein, the terms “use,” “using,” and “used” may be considered synonymous with the terms “utilize,” “utilizing,” and “utilized,” respectively. As used herein, expressions such as “at least one of,” “one of,” and “selected from,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Further, the use of “may” when describing embodiments of the present disclosure refers to “one or more embodiments of the present disclosure”.
Hereinafter, embodiments of the present disclosure will be explained by referring to the drawings.
The display apparatus DD may include a display panel DP and an optical layer PP disposed on the display panel DP. The display panel DP includes luminescence devices ED-1, ED-2 and ED-3. The display apparatus DD may include multiple luminescence devices ED-1, ED-2 and/or ED-3. The optical layer PP may be disposed on the display panel DP and may control or reduce reflection of external light by the display panel DP. The optical layer PP may include, for example, a polarization layer or a color filter layer. In some embodiments, different from the drawings, the optical layer PP may not be provided in the display apparatus DD of an embodiment.
On the optical layer PP, a base substrate BL may be disposed. The base substrate BL may be a member providing a base surface where the optical layer PP is disposed. The base substrate BL may be a glass substrate, a metal substrate, a plastic substrate, etc. However, embodiments of the present disclosure are not limited thereto, and the base substrate BL may be an inorganic layer, an organic layer or a composite material layer. In some embodiments, the base substrate BL may not be provided.
The display apparatus DD according to an embodiment may further include a plugging layer. The plugging layer may be disposed between a display device layer DP-ED and a base substrate BL. The plugging layer may be an organic layer. The plugging layer may include at least one selected from among an acrylic resin, a silicon-based resin and an epoxy-based resin.
The display panel DP may include a base layer BS, a circuit layer DP-CL provided on the base layer BS and a display device layer DP-ED. The display device layer DP-ED may include a pixel definition layer PDL, luminescence devices ED-1, ED-2 and ED-3 disposed in the pixel definition layer PDL, and an encapsulating layer TFE disposed on the luminescence devices ED-1, ED-2 and ED-3.
The base layer BS may be a member providing a base surface where the display device layer DP-ED is disposed. The base layer BS may be a glass substrate, a metal substrate, a plastic substrate, etc. However, embodiments of the present disclosure are not limited thereto, and the base layer BS may be an inorganic layer, an organic layer or a composite material layer.
In an embodiment, the circuit layer DP-CL is disposed on the base layer BS, and the circuit layer DP-CL may include multiple transistors. Each of the transistors may include a control electrode, an input electrode, and an output electrode. For example, the circuit layer DP-CL may include switching transistors and driving transistors for driving the luminescence devices ED-1, ED-2 and ED-3 of the display device layer DP-ED.
Each of the luminescence devices ED-1, ED-2 and ED-3 may have the structures of any of the luminescence devices ED of embodiments according to
In
An encapsulating layer TFE may cover the luminescence devices ED-1, ED-2 and ED-3. The encapsulating layer TFE may encapsulate the display device layer DP-ED. The encapsulating layer TFE may be a thin film encapsulating layer. The encapsulating layer TFE may be one layer or a stacked layer of multiple layers. The encapsulating layer TFE includes at least one insulating layer. The encapsulating layer TFE according to an embodiment may include at least one inorganic layer (hereinafter, encapsulating inorganic layer). In some embodiments, the encapsulating layer TFE according to an embodiment may include at least one organic layer (hereinafter, encapsulating organic layer) and at least one encapsulating inorganic layer.
The encapsulating inorganic layer protects the display device layer DP-ED from moisture/oxygen, and the encapsulating organic layer protects the display device layer DP-ED from foreign materials (such as dust particles). The encapsulating inorganic layer may include silicon nitride, silicon oxy nitride, silicon oxide, titanium oxide, and/or aluminum oxide, without specific limitation. The encapsulating organic layer may include an acrylic compound, an epoxy-based compound, etc. The encapsulating organic layer may include a photopolymerizable organic material, without specific limitation.
The encapsulating layer TFE may be disposed on the second electrode EL2 and may be disposed while filling the opening portion OH.
Referring to
The luminous areas PXA-R, PXA-G and PXA-B may be areas separated by the pixel definition layer PDL. The non-luminous areas NPXA may be areas between neighboring luminous areas PXA-R, PXA-G and PXA-B and may be areas corresponding to the pixel definition layer PDL. In some embodiments, each of the luminous areas PXA-R, PXA-G and PXA-B may correspond to a pixel. The pixel definition layer PDL may divide the luminescence devices ED-1, ED-2 and ED-3. The emission layers EML-R, EML-G and EML-B of the luminescence devices ED-1, ED-2 and ED-3 may be disposed and divided in the opening portions OH defined in the pixel definition layer PDL.
The luminous areas PXA-R, PXA-G and PXA-B may be divided into multiple groups according to the color of light produced from the luminescence devices ED-1, ED-2 and ED-3. In the display apparatus DD of an embodiment, shown in
In the display apparatus DD according to an embodiment, multiple luminescence devices ED-1, ED-2 and ED-3 may be to emit light having different wavelength regions. For example, in an embodiment, the display apparatus DD may include a first luminescence device ED-1 to emit red light, a second luminescence device ED-2 to emit green light, and a third luminescence device ED-3 to emit blue light. For example, the red luminous area PXA-R, the green luminous area PXA-G, and the blue luminous area PXA-B of the display apparatus DD may respectively correspond to the first luminescence device ED-1, the second luminescence device ED-2, and the third luminescence device ED-3.
However, embodiments of the present disclosure are not limited thereto, and the first to third luminescence devices ED-1, ED-2 and ED-3 may be to emit light in substantially the same wavelength region, or at least one thereof may be to emit light in a different wavelength region. For example, all the first to third luminescence devices ED-1, ED-2 and ED-3 may be to emit blue light.
The luminous areas PXA-R, PXA-G and PXA-B in the display apparatus DD according to an embodiment may be arranged in a stripe shape. Referring to
In
The arrangement type or pattern of the luminous areas PXA-R, PXA-G and PXA-B is not limited to the configuration shown in
In some embodiments, the areas of the luminous areas PXA-R, PXA-G and PXA-B may be different from each other. For example, in an embodiment, the area of the green luminous area PXA-G may be smaller than the area of the blue luminous area PXA-B, but embodiments of the present disclosure are not limited thereto.
Hereinafter,
The luminescence device ED of an embodiment may include an amine compound, which will be explained later, in the hole transport region HTR disposed between the first electrode EL1 and the second electrode EL2. However, embodiments of the present disclosure are not limited thereto, and the luminescence device ED of an embodiment may include a compound, which will be explained later, in an emission layer EML or an electron transport region ETR, which correspond to multiple functional layers disposed between the first electrode EL1 and the second electrode EL2, or in a capping layer CPL disposed on the second electrode EL2 in addition to the hole transport region HTR.
Compared with
The first electrode EL1 has conductivity. The first electrode EL1 may be formed utilizing a metal alloy or a conductive compound. The first electrode EL1 may be an anode or a cathode. However, embodiments of the present disclosure are not limited thereto. In some embodiments, the first electrode EL1 may be a pixel electrode. The first electrode EL1 may be a transmissive electrode, a transflective electrode, or a reflective electrode. When the first electrode EL1 is a transmissive electrode, the first electrode EL1 may include a transparent metal oxide (such as indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), and/or indium tin zinc oxide (ITZO)). When the first electrode EL1 is a transflective electrode or a reflective electrode, the first electrode EL1 may include silver (Ag), magnesium (Mg), copper (Cu), aluminum (Al), platinum (Pt), palladium (Pd), gold (Au), nickel (Ni), neodymium (Nd), iridium (Ir), chromium (Cr), lithium (Li), calcium (Ca), LiF/Ca, LiF/Al, molybdenum (Mo), titanium (Ti), one or more compounds thereof, or one or more mixtures thereof (for example, a mixture of Ag and Mg). In some embodiments, the first electrode EL1 may have a structure of multiple layers including a reflective layer or a transflective layer formed utilizing the above materials, and a transmissive conductive layer formed utilizing ITO, IZO, ZnO, or ITZO. For example, the first electrode EL1 may include a three-layer structure of ITO/Ag/ITO. However, embodiments of the present disclosure are not limited thereto. The thickness of the first electrode EL1 may be about 700 Å to about 10,000 Å. For example, the thickness of the first electrode EL1 may be about 1,000 Å to about 3,000 Å.
The hole transport region HTR is provided on the first electrode EL1. The hole transport region HTR may include at least one selected from among a hole injection layer HIL, a hole transport layer HTL, a hole buffer layer, and an electron blocking layer EBL. The thickness of the hole transport region HTR may be, for example, about 50 Å to about 15,000 Å.
The hole transport region HTR may have a single layer formed utilizing a single material, a single layer formed utilizing multiple different materials, or a multilayer structure including multiple layers formed utilizing multiple different materials.
For example, the hole transport region HTR may have the structure of a single layer of a hole injection layer HIL or a hole transport layer HTL, and may have a structure of a single layer formed utilizing a hole injection material and a hole transport material. In some embodiments, the hole transport region HTR may have a structure of a single layer formed utilizing multiple different materials, or a structure stacked from the first electrode EL1 of hole injection layer HIL/hole transport layer HTL, hole injection layer HIL/hole transport layer HTL/hole buffer layer, hole injection layer HIL/hole buffer layer, hole transport layer HTL/hole buffer layer, or hole injection layer HIL/hole transport layer HTL/electron blocking layer EBL, without limitation.
The hole transport region HTR of the luminescence device ED of an embodiment may include an amine compound according to embodiments of the present disclosure.
In the description, the term “substituted or unsubstituted” refers to being unsubstituted, or substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a silyl group, an oxy group, a thio group, a sulfinyl group, a sulfonyl group, a carbonyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkenyl group, an alkoxy group, a hydrocarbon ring group, an aryl group, and a heterocyclic group. Each of the exemplified substituents may be further substituted or unsubstituted. For example, a biphenyl group may be interpreted as a named aryl group, or as a phenyl group substituted with a phenyl group.
In the description, the halogen atom may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
In the description, the alkyl group may be a linear, branched or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Examples of the alkyl group may include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, i-butyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, i-pentyl, neopentyl, t-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, t-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldocecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-henicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, etc., without limitation.
In the description, the term “alkenyl group” may refer to a hydrocarbon group including one or more carbon double bonds in the middle or at the terminal of an alkyl group of 2 or more carbon atoms. The alkenyl group may be a linear chain or a branched chain. The carbon number is not specifically limited but may be 2 to 30, 2 to 20, or 2 to 10. Examples of the alkenyl group may include a vinyl group, a 1-butenyl group, a 1-pentenyl group, a 1,3-butadienyl aryl group, a styrenyl group, a styrylvinyl group, etc., without limitation.
In the description, the term “alkynyl group” may refer to a hydrocarbon group including one or more carbon triple bonds in the middle or at the terminal of an alkyl group of 2 or more carbon atoms. The alkynyl group may be a linear chain or a branched chain. The carbon number is not specifically limited but may be 2 to 30, 2 to 20, or 2 to 10. Examples of the alkynyl group may include an ethynyl group, a propynyl group, etc., without limitation.
In the description, the term “hydrocarbon ring group” refers to an optional functional group or substituent derived from an aliphatic hydrocarbon ring, or an optional functional group or substituent derived from an aromatic hydrocarbon ring. The carbon number for forming rings of the hydrocarbon ring group may be 5 to 60, 5 to 30, or 5 to 20.
In the description, the term “aryl group” refers to an optional functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The carbon number for forming rings in the aryl group may be 6 to 30, 6 to 20, or 6 to 15. Examples of the aryl group may include phenyl, naphthyl, fluorenyl, anthracenyl, phenanthryl, biphenyl, terphenyl, quaterphenyl, quinquephenyl, sexiphenyl, triphenylenyl, pyrenyl, benzofluoranthenyl, chrysenyl, etc., without limitation.
In the description, the fluorenyl group may be substituted (e.g., at the 9H position), and two substituents may be combined with each other to form a spiro structure. Examples of a substituted fluorenyl group are as follows. However, embodiments of the present disclosure are not limited thereto.
In the description, the term “heterocyclic group” may refer to an optional functional group or substituent derived from a ring including one or more among boron (B), oxygen (O), nitrogen (N), phosphorus (P), silicon (Si) and sulfur (S) as heteroatoms. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. The aromatic heterocyclic group may be a heteroaryl group. The aliphatic heterocyclic group and the aromatic heterocyclic group may be a monocycle or a polycycle.
In the description, the heterocyclic group may include one or more among B, O, N, P, Si and S as heteroatoms. When the heterocyclic group includes two or more heteroatoms, the two or more heteroatoms may be the same or different. The heterocyclic group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group and has the concept including a heteroaryl group. The carbon number for forming rings of the heterocyclic group may be 2 to 30, 2 to 20, or 2 to 10.
In the description, the aliphatic heterocyclic group may include one or more among B, O, N, P, Si and S as heteroatoms. The carbon number for forming rings of the aliphatic heterocyclic group may be 2 to 30, 2 to 20, or 2 to 10. Examples of the aliphatic heterocyclic group may include an oxirane group, a thiirane group, a pyrrolidine group, a piperidine group, a tetrahydrofuran group, a tetrahydrothiophene group, a thiane group, a tetrahydropyran group, a 1,4-dioxane group, etc., without limitation.
In the description, the heteroaryl group may include one or more among B, O, N, P, Si and S as heteroatoms. When the heteroaryl group includes two or more heteroatoms, two or more heteroatoms may be the same or different. The heteroaryl group may be a monocyclic heterocyclic group or polycyclic heterocyclic group. The carbon number for forming rings of the heteroaryl group may be 2 to 30, 2 to 20, or 2 to 10. Examples of the heteroaryl group may include thiophene, furan, pyrrole, imidazole, triazole, pyridine, bipyridine, pyrimidine, triazine, acridyl, pyridazine, pyrazinyl, quinoline, quinazoline, quinoxaline, phenoxazine, phthalazine, pyrido pyrimidine, pyrido pyrazine, pyrazino pyrazine, isoquinoline, indole, carbazole, N-arylcarbazole, N-heteroarylcarbazole, N-alkylcarbazole, benzoxazole, benzimidazole, benzothiazole, benzocarbazole, benzothiophene, dibenzothiophene, thienothiophene, benzofuran, phenanthroline, thiazole, isooxazole, oxazole, oxadiazole, thiadiazole, phenothiazine, dibenzosilole, dibenzofuran, etc., without limitation.
In the description, the carbon number of the amine group is not specifically limited, but may be 1 to 30. The amine group may include an alkyl amine group, an aryl amine group, or a heteroaryl amine group. Examples of the amine group may include a methylamine group, a dimethylamine group, a phenylamine group, a diphenylamine group, a naphthylamine group, a 9-methyl-anthracenylamine group, a triphenylamine group, etc., without limitation.
In the description, the explanation on the aryl group may be applied to the arylene group except that the arylene group is a divalent group.
In the description, the explanation on the heteroaryl group may be applied to the heteroarylene group except that the heteroarylene group is a divalent group.
In some embodiments, in the description, “” refers to a position to be connected.
The amine compound according to embodiments of the present disclosure are represented by Formula 1.
In Formula 1, R1 is represented by Formula 2-1, and R2 and R3 are each independently represented by Formula 2-2 or Formula 2-3.
In Formula 2-1, X may be O or S.
In Formula 2-1, Ra to Rd may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where any one selected from among Ra to Rd may be a site bonded to nitrogen of Formula 1.
In Formula 2-1, any one selected from among Re to Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded.
In Formula 2-1, when Rd is bonded to the nitrogen of Formula 1, Re may be a hydrogen atom or a deuterium atom, or combined with adjacent Rf to form a ring.
*-(L1)m-Ar1. Formula 2-2
In Formula 2-2, L1 may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms.
In Formula 2-2, Ar1 may be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, where a fluorenyl group is excluded. In some embodiments, when R2 and R3 in Formula 1 are represented by Formula 2-2 at the same time (e.g., simultaneously), Ar1 is not a 1-naphthyl group.
In Formula 2-2, “m” may be an integer of 0 to 3, and when “m” is 2 or more, multiple L1 groups may each independently be the same or different.
In Formula 2-3, Y may be O or S.
In Formula 2-3, L2 may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms.
In Formula 2-3, R4 may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring.
In Formula 2-3, R5 may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring.
In Formula 2-3, “n” and “p” may each independently be an integer of 0 to 3. In some embodiments, when “n” is 2 or more, multiple L2 groups may each independently be the same or different, and when “p” is 2 or more, multiple R4 groups may each independently be the same or different.
In Formula 2-3, “q” may be an integer of 0 to 4. In some embodiments, when “q” is 2 or more, multiple R5 groups may each independently be the same or different.
Here, Formula 2-1 and Formula 2-3 are always different.
In some embodiments, when Ra of Formula 2-1 is bonded to the nitrogen of Formula 1, and Rh is an alkyl group or an aryl group, at least one selected from among R2 and R3 of Formula 1 may be represented by Formula 2-3. In this case, when X of Formula 2-1 is S, Formula 2-3 is not a 4-dibenzothiophenyl group.
The amine compound represented by Formula 1 according to an embodiment includes a compound in which optional hydrogen in a molecule is substituted with deuterium.
In an embodiment, in Formula 1, R1 may be represented by Formula 2-1-1, R2 may be represented by Formula 2-3, and R3 may be represented by Formula 2-2 or Formula 2-3.
In Formula 2-1-1, X may be O or S, and Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms.
In Formula 2-1-1, Rb to Rg may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring.
In an embodiment, in Formula 1, R1 may be represented by Formula 2-1-2, R2 may be represented by Formula 2-2, and R3 may be represented by Formula 2-2 or Formula 2-3.
In Formula 2-1-2, X may be O or S, and Ri may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rg group to form a ring.
In Formula 2-1-2, Rb to Rd may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring.
In Formula 2-1-2, any one selected from among Re to Rg may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded.
In an embodiment, in Formula 1, R1 may be represented by Formula 2-1-3, and R2 and R3 may be represented by Formula 2-2 or Formula 2-3.
In Formula 2-1-3, X may be O or S, and Re may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rf group to form a ring.
In Formula 2-1-3, Ra to Re may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring.
In Formula 2-1-3, any one selected from among Rf to Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded.
In an embodiment, Formula 1 may be represented by Formula 3-1 or Formula 3-2.
In Formula 3-1 and Formula 3-2, Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms.
In Formula 3-1 and Formula 3-2, Rb to Rg may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring.
In Formula 3-2, Y′ may be O or S, L2′ may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms.
In Formula 3-2, R4′ may be a hydrogen atom, a deuterium atom, a halogen atom, or a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, and/or combined with an adjacent group to form a ring.
In Formula 3-2, R5′ may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring.
In Formula 3-2, n′ and p′ may each independently be an integer of 0 to 3. In some embodiments, when n′ is 2 or more, multiple L2 groups may each independently be the same or different, and when p′ is 2 or more, multiple R4′ groups may each independently be the same or different.
In Formula 3-2, q′ may be an integer of 0 to 4. In some embodiments, when q′ is 2 or more, multiple R5′ groups may each independently be the same or different.
In Formula 3-1 and Formula 3-2, X, Ar1, Y, L1, L2, R4, R5, “m”, “n”, “p” and “q” may each independently be the same as defined in Formula 2-1 to Formula 2-3.
In an embodiment, Formula 1 may be represented by any one selected from among Formula 4-1 to Formula 4-3.
In Formula 4-1 to Formula 4-3, Ri may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rg group to form a ring.
In Formula 4-1 to Formula 4-3, Rb to Rd may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring.
In Formula 4-1 to Formula 4-3, any one selected from among Re to Rg may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded.
In Formula 4-1 to Formula 4-3, L1′ and L2′ may each independently be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms.
In Formula 4-1, Ar1′ may be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, where a fluorenyl group is excluded.
In Formula 4-1, m′ may be an integer of 0 to 3. In some embodiments, when m′ is 2 or more, multiple L1′ groups may each independently be the same or different.
In Formula 4-1 and Formula 4-2, Ar1 may be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, where a fluorenyl group is excluded. Here, in Formula 4-1, Ar1 and Ar1′ are not 1-naphthyl groups at the same time (e.g., simultaneously).
In Formula 4-3, R4′ may be a hydrogen atom, a deuterium atom, a halogen atom, or a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, and/or combined with an adjacent group to form a ring, and R5′ may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring.
In Formula 4-3, n′ and p′ may each independently be an integer of 0 to 3. In some embodiments, when n′ is 2 or more, multiple L2′ groups may each independently be the same or different, and when p′ is 2 or more, multiple R4′ groups may each independently be the same or different.
In Formula 4-3, q′ may be an integer of 0 to 4. In some embodiments, when q′ is 2 or more, multiple R5′ groups may each independently be the same or different.
In Formula 4-1 to Formula 4-3, X, Y, L1, L2, R4, R5, “m”, “n”, “p” and “q” may each independently be the same as defined in Formula 2-1 to Formula 2-3.
In an embodiment, Formula 1 may be represented by any one selected from among Formula 5-1 to Formula 5-3.
In Formula 5-1 to Formula 5-3, Re may be a hydrogen atom or a deuterium atom, or combined with an adjacent Rf group to form a ring.
In Formula 5-1 to Formula 5-3, Ra to Re may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, and any one selected from among Rf to Rh may be a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and the remainder may each independently be a hydrogen atom, a deuterium atom, or a halogen atom, or combined with an adjacent group to form a ring, where a fluorenyl group is excluded.
In Formula 5-1, L1′ may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms.
In Formula 5-1, Ar1′ may be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, where a fluorenyl group is excluded.
In Formula 5-1, m′ may be an integer of 0 to 3. In some embodiments, when m′ is 2 or more, multiple L1′ groups may each independently be the same or different.
In Formula 5-1 and Formula 5-2, Ar1 may be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, where a fluorenyl group is excluded. In Formula 5-1, Ar1 and Ar1′ are not 1-naphthyl groups at the same time (e.g., simultaneously).
In Formula 5-3, Y′ may be O or S, and L2′ may be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms.
In Formula 5-3, R4′ may be a hydrogen atom, a deuterium atom, a halogen atom, or a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, and/or combined with an adjacent group to form a ring.
In Formula 5-3, R5′ may be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring.
In Formula 5-3, n′ and p′ may each independently be an integer of 0 to 3. When n′ is 2 or more, multiple L2′ groups may each independently be the same or different, and when p′ is 2 or more, multiple R4′ groups may each independently be the same or different.
In Formula 5-3, q′ may be an integer of 0 to 4. In some embodiments, when q′ is 2 or more, multiple R5′ groups may each independently be the same or different.
In Formula 5-1 to Formula 5-3, X, Y, L1, L2, R4, R5, “m”, “n”, “p” and “q” may each independently be the same as defined in Formula 2-1 to Formula 2-3.
In an embodiment, the amine compound represented by Formula 1 may not include an (e.g., additional) amine group other than the amine group represented by Formula 1. For example, the amine compound represented by Formula 1 may be a monoamine compound.
In an embodiment, the amine compound represented by Formula 1 may not include an N-containing heteroaryl group.
In an embodiment, L1 and L2 of Formula 2-2 and Formula 2-3 may be each independently a direct linkage, a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent biphenyl group or a substituted or unsubstituted naphthylenyl group.
In an embodiment, Rh may be a substituted or unsubstituted phenyl group.
The amine compound represented by Formula 1 according to an embodiment may be any one selected from among the compounds represented in Compound Group 1 to Compound Group 3. However, embodiments of the present disclosure are not limited thereto.
Referring to
As described above, the hole transport region HTR includes the aforementioned amine compound according to embodiments of the present disclosure. For example, the hole transport region HTR includes the amine compound represented by Formula 1.
When the hole transport region HTR has a multilayer structure having multiple layers, any one layer among the multiple layers may include the amine compound represented by Formula 1. For example, a hole transport region HTR may include a hole injection layer HIL disposed on a first electrode EL1 and a hole transport layer HTL disposed on the hole injection layer HIL, and the hole transport layer HTL may include the amine compound represented by Formula 1. However, embodiments of the present disclosure are not limited thereto, and for example, the hole injection layer HIL may include the amine compound represented by Formula 1.
The hole transport region HTR may include one or two or more types (kinds) of the amine compound represented by Formula 1. For example, the hole transport region HTR may include at least one selected from the compounds represented in Compound Groups 1 to 3.
The hole transport region HTR may be formed utilizing various suitable methods (such as a vacuum deposition method, a spin coating method, a cast method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, and/or a laser induced thermal imaging (LITI) method).
The hole transport region HTR may include a compound represented by Formula H-1.
In Formula H-1, L1 and L2 may each independently be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms. “a” and “b” may each independently be an integer of 0 to 10. In some embodiments, when “a” or “b” is an integer of 2 or more, multiple L1 and L2 may each independently be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms.
In Formula H-1, Ar1 and Ar2 may each independently be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms. In Formula H-1, Ar3 may be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms.
The compound represented by Formula H-1 may be a monoamine compound. In some embodiments, the compound represented by Formula H-1 may be a diamine compound in which at least one selected from among Ar1 to Ar3 includes an amine group as a substituent. In some embodiments, the compound represented by Formula H-1 may be a carbazole-based compound in which at least one selected from among Ar1 to Ar3 includes a substituted or unsubstituted carbazole group, or a fluorene-based compound in which at least one selected from among Ar1 to Ar3 includes a substituted or unsubstituted fluorene group.
The compound represented by Formula H-1 may be represented by any one selected from among the compounds in Compound Group H. However, the compounds shown in Compound Group H are only illustrations, and the compound represented by Formula H-1 is not limited to the compounds represented in Compound Group H.
The hole transport region HTR may include a phthalocyanine compound (such as copper phthalocyanine), N1,N1′-([1,1′-biphenyl]-4,4′-diyl)bis(N1-phenyl-N4,N4-di-m-tolylbenzene-1,4-diamine) (DNTPD), 4,4′,4″-[tris(3-methylphenyl)phenylamino]triphenylamine (m-MTDATA), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (TDATA), 4,4′,4″-tris[N(1-naphthyl)-N-phenylamino]-triphenylamine (1-TNATA), 4,4′,4″-tris[N(2-naphthyl)-N-phenylamino]-triphenylamine (2-TNATA), poly(3,4-ethylene dioxythiophene)/poly(4-styrene sulfonate) (PEDOT/PSS), polyaniline/dodecylbenzene sulfonic acid (PANI/DBSA), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrene sulfonate) (PANI/PSS), N,N′-di(1-naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB), triphenylamine-containing polyether ketone (TPAPEK), 4-isopropyl-4′-methyldiphenyliodonium [tetrakis(pentafluorophenyl)borate], and dipyrazino[2,3-f:2′,3′-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile (HAT-CN).
The hole transport region HTR may include, for example, carbazole derivatives (such as N-phenyl carbazole and/or polyvinyl carbazole), fluorene-based derivatives, N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (TPD), triphenylamine-based derivatives (such as 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA)), N,N′-di(1-naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB), 4,4′-cyclohexylidene bis[N,N-bis(4-methylphenyl)benzeneamine (TAPC), 4,4′-bis[N,N′-(3-tolyl)amino]-3,3′-dimethylbiphenyl (HMTPD), 1,3-bis(N-carbazolyl)benzene (mCP), etc.
The hole transport region HTR may include 9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole (CzSi), 9-phenyl-9H-3,9′-bicarbazole (CCP), 1,3-bis(1,8-dimethyl-9H-carbazol-9-yl)benzene (mDCP), etc.
The hole transport region HTR may include the compounds of the hole transport region in at least one selected from among the hole injection layer HIL, hole transport layer HTL, and electron blocking layer EBL.
The thickness of the hole transport region HTR may be about 100 Å to about 10,000 Å, for example, about 100 Å to about 5,000 Å. The thickness of the hole injection region HIL may be, for example, about 30 Å to about 1,000 Å. The thickness of the hole transport layer HTL may be about 30 Å to about 1,000 Å. For example, the thickness of the electron blocking layer EBL may be about 10 Å to about 1,000 Å. When the thicknesses of the hole transport region HTR, the hole injection layer HIL, the hole transport layer HTL and the electron blocking layer EBL satisfy the above-described ranges, satisfactory hole transport properties may be achieved without substantial increase of a driving voltage.
The hole transport region HTR may further include a charge generating material to increase conductivity in addition to the above-described materials. The charge generating material may be dispersed substantially uniformly or non-uniformly in the hole transport region HTR. The charge generating material may be, for example, a p-dopant. The p-dopant may include any one selected from among quinone derivatives, metal oxides, and cyano group-containing compounds, without limitation. For example, non-limiting examples of the p-dopant may include quinone derivatives (such as tetracyanoquinodimethane (TCNQ) and/or 2,3,5,6-tetrafluoro-7,7′,8,8-tetracyanoquinodimethane (F4-TCNQ)), metal oxides (such as tungsten oxide and/or molybdenum oxide), etc., without limitation.
As described above, the hole transport region HTR may further include at least one of a hole buffer layer or an electron blocking layer EBL in addition to the hole injection layer HIL and the hole transport layer HTL. The hole buffer layer may compensate for a resonance distance of the wavelength of light emitted from an emission layer EML, and may thereby increase the light emitting efficiency of the device. As materials included in the hole buffer layer, materials that may be included in the hole transport region HTR may be utilized. The electron blocking layer EBL may block or reduce the injection of electrons from an electron transport region ETR to a hole transport region HTR.
The emission layer EML is provided on the hole transport region HTR. The emission layer EML may have a thickness of, for example, about 100 Å to about 1,000 Å or about 100 Å to about 300 Å. The emission layer EML may have a single layer formed utilizing a single material, a single layer formed utilizing multiple different materials, or a multilayer structure having multiple layers formed utilizing multiple different materials.
In the luminescence device ED of an embodiment, the emission layer EML may include anthracene derivatives, pyrene derivatives, fluoranthene derivatives, chrysene derivatives, dihydrobenzanthracene derivatives, and/or triphenylene derivatives. For example, the emission layer EML may further include anthracene derivatives and/or pyrene derivatives.
In the luminescence devices ED of embodiments, shown in
In Formula E-1, R31 to R40 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkyl group of 1 to 10 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring. In some embodiments, R31 to R40 may be combined with an adjacent group to form a saturated hydrocarbon ring or an unsaturated hydrocarbon ring.
In Formula E-1, “c” and “d” may be an integer of 0 to 5.
Formula E-1 may be represented by any one selected from among Compound E1 to Compound E19.
In an embodiment, the emission layer EML may include a compound represented by Formula E-2a or Formula E-2b. The compound represented by Formula E-2a or Formula E-2b may be utilized as a phosphorescence host material.
In Formula E-2b, “a” may be an integer of 0 to 10, and La may be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms. In some embodiments, when “a” is an integer of 2 or more, multiple La may each independently be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms.
In some embodiments, in Formula E-2a, A1 to A5 may each independently be N or CRi. Ra to Ri may each independently be a hydrogen atom, a deuterium atom, a substituted or unsubstituted amine group, a substituted or unsubstituted thio group, a substituted or unsubstituted oxy group, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group of 2 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms, and/or may be combined with an adjacent group to form a ring. Ra to Ri may be combined with an adjacent group to form a hydrocarbon ring or a heterocycle including N, O, S, etc. as a ring-forming atom.
In some embodiments, in Formula E-2a, two or three selected from A1 to A5 may be N, and the remainder may be CRi.
In Formula E-2b, Cbz1 and Cbz2 may each independently be an unsubstituted carbazole group, or a carbazole group substituted with an aryl group of 6 to 30 ring-forming carbon atoms. Lb may be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms. “b” may be an integer of 0 to 10, and when “b” is an integer of 2 or more, multiple Lb may each independently be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms.
The compound represented by Formula E-2a or Formula E-2b may be represented by any one selected from among the compounds in Compound Group E-2. However, the compounds shown in Compound Group E-2 are only illustrations, and the compound represented by Formula E-2a or Formula E-2b is not limited to the compounds represented in Compound Group E-2.
The emission layer EML may further include a common material well-known in the art as a host material. For example, the emission layer EML may include as a host material, at least one of bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO), 4,4′-bis(carbazol-9-yl)-1,1′-biphenyl (CBP), 1,3-bis(carbazol-9-yl)benzene (mCP), 2,8-bis(diphenylphosphoryl)dibenzo[b,d]furan (PPF), 4,4′,4″-tris(carbazol-9-yl)-triphenylamine (TCTA), or 1,3,5-tris(1-phenyl-1H-benzo[d]imidazole-2-yl)benzene (TPBi). However, embodiments of the present disclosure are not limited thereto. For example, tris(8-hydroxyquinolino)aluminum (Alq3), 9,10-di(naphthalene-2-yl)anthracene (ADN), 2-tert-butyl-9,10-di(naphth-2-yl)anthracene (TBADN), distyrylarylene (DSA), 4,4′-bis(9-carbazolyl)-2,2′-dimethyl-biphenyl (CDBP), 2-methyl-9,10-bis(naphthalen-2-yl)anthracene (MADN), hexaphenyl cyclotriphosphazene (CP1), 1,4-bis(triphenylsilyl)benzene (UGH2), hexaphenylcyclotrisiloxane (DPSiO3), octaphenylcyclotetra siloxane (DPSiO4), etc. may be utilized as the host material.
The emission layer EML may include a compound represented by Formula M-a or Formula M-b. The compound represented by Formula M-a or Formula M-b may be utilized as a phosphorescence dopant material.
In Formula M-a, Y1 to Y4, and Z1 to Z4 may each independently be CR1 or N, and R1 to R4 may each independently be a hydrogen atom, a deuterium atom, a substituted or unsubstituted amine group, a substituted or unsubstituted thio group, a substituted or unsubstituted oxy group, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group of 2 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms, and/or may be combined with an adjacent group to form a ring. In Formula M-a, “m” may be 0 or 1, and “n” may be 2 or 3. In Formula M-a, when “m” is 0, “n” is 3, and when “m” is 1, “n” is 2.
The compound represented by Formula M-a may be utilized as a red phosphorescence dopant or a green phosphorescence dopant.
The compound represented by Formula M-a may be represented by any one selected from among Compounds M-a1 to M-a25. However, Compounds M-a1 to M-a25 are illustrations, and the compound represented by Formula M-a is not limited to the compounds represented by Compounds M-a1 to M-a25.
Compound M-a1 and Compound M-a2 may be utilized as red dopant materials, and Compound M-a3 and Compound M-a4 may be utilized as green dopant materials.
In Formula M-b, Q1 to Q4 may each independently be C or N, C1 to C4 may each independently be a substituted or unsubstituted hydrocarbon ring of 5 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heterocycle of 2 to 30 ring-forming carbon atoms. L21 to L24 may each independently be a direct linkage,
a substituted or unsubstituted divalent alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms, and e1 to e4 may each independently be 0 or 1. R31 to R39 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted amine group, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring, and d1 to d4 may each independently be an integer of 0 to 4.
The compound represented by Formula M-b may be utilized as a blue phosphorescence dopant or a green phosphorescence dopant.
The compound represented by Formula M-b may be represented by any one selected from among the compounds below. However, the compounds below are illustrations, and the compound represented by Formula M-b is not limited to the compounds represented below.
In the compounds above, R, R38, and R39 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted amine group, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms.
The emission layer EML may include any one selected from among Formula F-a to Formula F-c. The compounds represented by Formula F-a to Formula F-c may be utilized as fluorescence dopant materials.
In Formula F-a, two selected from Ra to Rj may each independently be substituted with *—NAr1Ar2. The remainder not substituted with *—NAr1Ar2 among Ra to Rj may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted amine group, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms.
In *—NAr1Ar2, Ar1 and Ar2 may each independently be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms. For example, at least one selected from among Ar1 and Ar2 may be a heteroaryl group including O or S as a ring-forming atom.
In Formula F-b, Ra and Rb may each independently be a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group of 2 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms, and/or may be combined with an adjacent group to form a ring. Ar1 to Ar4 may each independently be a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms.
In Formula F-b, U and V may each independently be 0 or 1. In Formula F-b, U refers to the number of rings combined at position U, and V refers to the number of rings combined at position V. For example, when the number of U or V is 1, the ring designated by U or V forms a fused ring, and when U or V is 0, the ring designated by U or V is not present. For example, when U is 0, and V is 1, or when U is 1, and V is 0, a fused ring having the fluorene core of Formula F-b may be a ring compound with four rings. In some embodiments, when both (e.g., simultaneously) U and V are 0, the fused ring of Formula F-b may be a ring compound with three rings. In some embodiments, when both (e.g., simultaneously) U and V are 1, a fused ring having the fluorene core of Formula F-b may be a ring compound with five rings.
In Formula F-b, when U or V is 1, U and V may each independently be a substituted or unsubstituted hydrocarbon ring of 5 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heterocycle of 2 to 30 ring-forming carbon atoms.
In Formula F-c, A1 and A2 may each independently be O, S, Se, or NRm, and Rm may be a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms. R1 to R11 may each independently be a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a substituted or unsubstituted amine group, a substituted or unsubstituted boryl group, a substituted or unsubstituted oxy group, a substituted or unsubstituted thio group, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms, and/or combined with an adjacent group to form a ring.
In Formula F-c, A1 and A2 may each independently be combined with the substituents of an adjacent ring to form a fused ring. For example, when A1 and A2 may be each independently NRm, A1 may be combined with R4 or R5 to form a ring. In some embodiments, A2 may be combined with R7 or R8 to form a ring.
In an embodiment, the emission layer EML may include, as a suitable dopant material, styryl derivatives (for example, 1,4-bis[2-(3-N-ethylcarbazolyl)vinyl]benzene (BCzVB), 4-(di-p-tolylamino)-4′-[(di-p-tolylamino)styryl]stilbene (DPAVB), and N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine (N-BDAVBi), perylene and/or derivatives thereof (for example, 2,5,8,11-tetra-t-butylperylene (TBP)), pyrene and/or derivatives thereof (for example, 1,1-dipyrene, 1,4-dipyrenylbenzene, and/or 1,4-bis(N,N-diphenylamino)pyrene), etc.
The emission layer EML may include a suitable phosphorescence dopant material. For example, the phosphorescence dopant may utilize a metal complex including iridium (Ir), platinum (Pt), osmium (Os), gold (Au), titanium (Ti), zirconium (Zr), hafnium (Hf), europium (Eu), terbium (Tb) or thulium (Tm). For example, iridium(III) bis(4,6-difluorophenylpyridinato-N,C2′)picolinate (Firpic), bis(2,4-difluorophenylpyridinato)-tetrakis(1-pyrazolyl)borate iridium(III) (Fir6), or platinum octaethyl porphyrin (PtOEP) may be utilized as the phosphorescence dopant. However, embodiments of the present disclosure are not limited thereto.
The emission layer EML may include a quantum dot material. The core of the quantum dot may be selected from a Group II-VI compound, a Group III-V compound, a Group IV-VI compound, a Group IV element, a Group IV compound, and combinations thereof.
The II-VI group compound may be selected from the group consisting of: a binary compound selected from the group consisting of CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, and mixtures thereof; a ternary compound selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, MgZnSe, MgZnS, and mixtures thereof; and a quaternary compound selected from the group consisting of HgZnTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.
The Group III-VI compound may include a binary compound (such as In2S3, and/or In2Se3), a ternary compound (such as InGaS3 and/or InGaSe3), or one or more optional combinations thereof.
The Group I-III-VI compound may be selected from a ternary compound selected from the group consisting of AgInS, AgInS2, CuInS, CuInS2, AgGaS2, CuGaS2, CuGaO2, AgGaO2, AgAlO2 and mixtures thereof, and a quaternary compound (such as AgInGaS2 and/or CuInGaS2).
The Group III-V compound may be selected from the group consisting of a binary compound selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof, a ternary compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InGaP, InAlP, InNP, InNAs, InNSb, InPAs, InPSb, and mixtures thereof, and a quaternary compound selected from the group consisting of GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GalnNSb, GaInPAs, GalnPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. In some embodiments, the Group III-V compound may further include a Group II metal. For example, InZnP, etc. may be selected as a Group III-II-V compound.
The Group IV-VI compound may be selected from the group consisting of a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof, a ternary compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof, and a quaternary compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof. The Group IV element may be selected from the group consisting of Si, Ge, and a mixture thereof. The Group IV compound may be a binary compound selected from the group consisting of SiC, SiGe, and a mixture thereof.
In this case, the binary compound, the ternary compound and/or the quaternary compound may each independently be present at a substantially uniform concentration in a particle, or may be present at a partially different (e.g., non-uniform) concentration distribution state in the same particle. In some embodiments, a core/shell structure in which one quantum dot wraps another quantum dot may be possible. The interface of the core and the shell may have a concentration gradient, in which the concentration of an element present in the shell is decreased toward the center.
In some embodiments, the quantum dot may have the above-described core-shell structure including a core including a nanocrystal and a shell wrapping the core. The shell of the quantum dot may play the role of a protection layer for preventing or reducing chemical deformation of the core to maintain semiconductor properties, and/or the role of a charging layer for imparting the quantum dot with electrophoretic properties. The shell may have a single layer or a multilayer. The interface of the core and shell may have concentration gradient of decreasing the concentration of elements present in the shell toward the center. Examples of the shell of the quantum dot may include a metal or non-metal oxide, a semiconductor compound, or combinations thereof.
For example, the metal or non-metal oxide may include a binary compound (such as SiO2, Al2O3, TiO2, ZnO, MnO, Mn2O3, Mn3O4, CuO, FeO, Fe2O3, Fe3O4, CoO, CO3O4 and/or NiO), and/or a ternary compound (such as MgAl2O4, CoFe2O4, NiFe2O4 and CoMn2O4), but embodiments of the present disclosure are not limited thereto.
In some embodiments, the semiconductor compound may include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnSeS, ZnTeS, GaAs, GaP, GaSb, HgS, HgSe, HgTe, InAs, InP, InGaP, InSb, AlAs, AlP, AlSb, etc., but embodiments of the present disclosure are not limited thereto.
The quantum dot may have a full width of half maximum (FWHM) of emission wavelength spectrum of about 45 nm or less, about 40 nm or less, more, about 30 nm or less. Within this range, color purity or color reproducibility may be improved. In some embodiments, light emitted via such quantum dot is emitted in all directions, and light view angle properties may be improved.
In some embodiments, the shape of the quantum dot may be any generally utilized shape in the art, without specific limitation. For example, the shape may be a spherical, pyramidal, multi-arm, or cubic nanoparticle, nanotube, nanowire, nanofiber, nanoplate particle, etc.
The quantum dot may control the color of light emitted, according to the particle size, and accordingly, the quantum dot may have one or more suitable emission colors (such as blue, red and green).
In the luminescence device ED of an embodiment, as shown in
The electron transport region ETR may have a single layer formed utilizing a single material, a single layer formed utilizing multiple different materials, or a multilayer structure having multiple layers formed utilizing multiple different materials.
For example, the electron transport region ETR may have a single layer structure of an electron injection layer EIL or an electron transport layer ETL, or a single layer structure formed utilizing an electron injection material and an electron transport material. Further, the electron transport region ETR may have a single layer structure formed utilizing multiple different materials, or a structure stacked from the emission layer EML of electron transport layer ETL/electron injection layer EIL, or hole blocking layer HBL/electron transport layer ETL/electron injection layer EIL, without limitation. The thickness of the electron transport region ETR may be, for example, about 1,000 Å to about 1,500 Å.
The electron transport region ETR may be formed utilizing one or more suitable methods (such as a vacuum deposition method, a spin coating method, a cast method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, and/or a laser induced thermal imaging (LITI) method).
The electron transport region ETR may include a compound represented by Formula ET-1.
In Formula ET-1, at least one selected from among X1 to X3 may be N, and the remainder may be CRa. Ra may be a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms. Ar1 to Ar3 may each independently be a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group of 1 to 20 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroaryl group of 2 to 30 ring-forming carbon atoms.
In Formula ET-1, “a” to “c” may each independently be an integer of 0 to 10. In Formula ET-1, L1 to L3 may each independently be a direct linkage, a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms. In some embodiments, when “a” to “c” are integers of 2 or more, L1 to L3 may each independently be a substituted or unsubstituted arylene group of 6 to 30 ring-forming carbon atoms, or a substituted or unsubstituted heteroarylene group of 2 to 30 ring-forming carbon atoms.
When the electron transport region ETR includes an electron transport layer ETL, the electron transport region ETR may include an anthracene-based compound. However, embodiments of the present disclosure are not limited thereto, and the electron transport region ETR may include, for example, tris(8-hydroxyquinolinato)aluminum (Alq3), 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene, 2,4,6-tris(3′-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine, 2-(4-(N-phenylbenzoimidazolyl-1-ylphenyl)-9,10-dinaphthylanthracene, 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)benzene (TPBi), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ), 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (tBu-PBD), bis(2-methyl-8-quinolinolato-N1,O8)-(1,1′-biphenyl-4-olato)aluminum (BAlq), beryllium bis(benzoquinolin-10-olate (Bebq2), 9,10-di(naphthalene-2-yl)anthracene (ADN), 1,3-bis[3,5-di(pyridin-3-yl)phenyl]benzene (BmPyPhB), or one or more mixtures thereof, without limitation.
The electron transport region ETR may include at least one selected from among Compounds ET1 to ET36.
In some embodiments, the electron transport region ETR may include a metal halide (such as LiF, NaCl, CsF, RbCl, RbI, CuI and/or KI), a lanthanide metal (such as Yb), or a co-depositing material of the metal halide and the lanthanide metal. For example, the electron transport region ETR may include KI:Yb, RbI:Yb, etc., as the co-depositing material. In some embodiments, the electron transport region ETR may utilize a metal oxide (such as Li2O and/or BaO), or 8-hydroxy-lithium quinolate (LiQ). However, embodiments of the present disclosure are not limited thereto. The electron transport region ETR also may be formed utilizing a mixture of an electron transport material and an insulating organo metal salt. The organo metal salt may be a material having an energy band gap of about 4 eV or more. For example, the organo metal salt may include, for example, metal acetates, metal benzoates, metal acetoacetates, metal acetylacetonates, and/or metal stearates. However, embodiments of the present disclosure are not limited thereto.
The electron transport region ETR may include the compounds of the electron transport region in at least one selected from among an electron injection layer EIL, an electron transport layer ETL, and a hole blocking layer HBL.
When the electron transport region ETR includes the electron transport layer ETL, the thickness of the electron transport layer ETL may be about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layer ETL satisfies the above-described range, satisfactory electron transport properties may be obtained without a substantial increase in driving voltage. When the electron transport region ETR includes the electron injection layer EIL, the thickness of the electron injection layer EIL may be about 1 Å to about 100 Å, and about 3 Å to about 90 Å. When the thickness of the electron injection layer EIL satisfies the above described range, satisfactory electron injection properties may be obtained without inducing substantial increase of a driving voltage.
The second electrode EL2 is provided on the electron transport region ETR. The second electrode EL2 may be a common electrode. The second electrode EL2 may be a cathode or an anode, but embodiments of the present disclosure are not limited thereto. For example, when the first electrode EL1 is an anode, the second cathode EL2 may be a cathode, and when the first electrode EL1 is a cathode, the second electrode EL2 may be an anode.
The second electrode EL2 may be a transmissive electrode, a transflective electrode or a reflective electrode. When the second electrode EL2 is a transmissive electrode, the second electrode EL2 may include a transparent metal oxide, for example, ITO, IZO, ZnO, ITZO, etc.
When the second electrode EL2 is a transflective electrode or a reflective electrode, the second electrode EL2 may include Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF/Ca, LiF/Al, Mo, Ti, Yb, W, one or more compounds thereof, or one or more mixtures thereof (for example, AgMg, AgYb, or MgAg). In some embodiments, the second electrode EL2 may have a multilayered structure including a reflective layer or a transflective layer formed utilizing the above-described materials and a transparent conductive layer formed utilizing ITO, IZO, ZnO, ITZO, etc. For example, the second electrode EL2 may include the aforementioned metal materials, combinations of two or more metal materials selected from the aforementioned metal materials, or oxides of the aforementioned metal materials.
In some embodiments, the second electrode EL2 may be connected with an auxiliary electrode. When the second electrode EL2 is connected with the auxiliary electrode, the resistance of the second electrode EL2 may decrease.
In some embodiments, a capping layer CPL may be further disposed on the second electrode EL2 in the luminescence device ED of an embodiment. The capping layer CPL may include a multilayer or a single layer.
In an embodiment, the capping layer CPL may be an organic layer or an inorganic layer. For example, when the capping layer CPL includes an inorganic material, the inorganic material may include an alkali metal compound (such as LiF), an alkaline earth metal compound (such as MgF2, SiON, SiNx, SiOy), etc.
For example, when the capping layer CPL includes an organic material, the organic material may include α-NPD, NPB, TPD, m-MTDATA, Alq3, CuPc, N4,N4,N4′,N4′-tetra(biphenyl-4-yl) biphenyl-4,4′-diamine (TPD15), 4,4′,4″-tris(carbazol sol-9-yl) triphenylamine (TCTA), etc., or includes an epoxy resin, or acrylate (such as methacrylate). In some embodiments, a capping layer CPL may include at least one selected from among Compounds P1 to P5, but embodiments of the present disclosure are not limited thereto.
In some embodiments, the refractive index of the capping layer CPL may be about 1.6 or more. For example, the refractive index of the capping layer CPL with respect to light in a wavelength range of about 550 nm to about 660 nm may be about 1.6 or more.
Referring to
In an embodiment shown in
The luminescence device ED may include a first electrode EL1, a hole transport region HTR disposed on the first electrode EL1, an emission layer EML disposed on the hole transport region HTR, an electron transport region ETR disposed on the emission layer EML, and a second electrode EL2 disposed on the electron transport region ETR. The structures of the luminescence devices of
Referring to
The light controlling layer CCL may be disposed on the display panel DP. The light controlling layer CCL may include a light converter. The light converter may be a quantum dot or a phosphor. The light converter may transform the wavelength of light provided and then emit (e.g., emit a different color light). For example, the light controlling layer CCL may be a layer including a quantum dot or a layer including a phosphor.
The light controlling layer CCL may include multiple light controlling parts CCP1, CCP2 and CCP3. The light controlling parts CCP1, CCP2 and CCP3 may be separated from one another.
Referring to
The light controlling layer CCL may include a first light controlling part CCP1 including a first quantum dot QD1 converting first color light provided from the luminescence device ED into second color light, a second light controlling part CCP2 including a second quantum dot QD2 converting first color light into third color light, and a third light controlling part CCP3 transmitting first color light.
In an embodiment, the first light controlling part CCP1 may provide red light (which is the second color light), and the second light controlling part CCP2 may provide green light (which is the third color light). The third color controlling part CCP3 may transmit and provide blue light (which is the first color light provided from the luminescence device ED). For example, the first quantum dot QD1 may be a red quantum dot, and the second quantum dot QD2 may be a green quantum dot. For the quantum dots QD1 and QD2, the same description as above may be applied.
In some embodiments, the light controlling layer CCL may further include a scatterer SP. The first light controlling part CCP1 may include the first quantum dot QD1 and the scatterer SP, the second light controlling part CCP2 may include the second quantum dot QD2 and the scatterer SP, and the third light controlling part CCP3 may not include a quantum dot but include the scatterer SP.
The scatterer SP may be an inorganic particle. For example, the scatterer SP may include at least one selected from among TiO2, ZnO, Al2O3, SiO2, and hollow silica. The scatterer SP may include at least one selected from among TiO2, ZnO, Al2O3, SiO2, and hollow silica, or may be a mixture of two or more materials selected from among TiO2, ZnO, Al2O3, SiO2, and hollow silica.
The light controlling layer CCL may include a barrier layer BFL1. The barrier layer BFL1 may play the role of blocking or reducing the penetration of moisture and/or oxygen (hereinafter, will be referred to as “humidity/oxygen”). The barrier layer BFL1 may be disposed on the light controlling parts CCP1, CCP2 and/or CCP3 to block or reduce the exposure of the light controlling parts CCP1, CCP2 and CCP3 to humidity/oxygen. In some embodiments, the barrier layer BFL1 may cover the light controlling parts CCP1, CCP2 and CCP3. In some embodiments, the barrier layer BFL2 may be provided between a color filter layer CFL and one or more of the light controlling parts CCP1, CCP2 and CCP3.
The barrier layers BFL1 and BFL2 may include at least one inorganic layer. For example, the barrier layers BFL1 and BFL2 may be formed by including an inorganic material. For example, the barrier layers BFL1 and BFL2 may be formed by including silicon nitride, aluminum nitride, zirconium nitride, titanium nitride, hafnium nitride, tantalum nitride, silicon oxide, aluminum oxide, titanium oxide, tin oxide, cerium oxide, silicon oxynitride and/or a metal thin film for securing light transmittance. In some embodiments, the barrier layers BFL1 and BFL2 may further include an organic layer. The barrier layers BFL1 and BFL2 may be composed of a single layer of multiple layers.
In the display apparatus DD of an embodiment, the color filter layer CFL may be disposed on the light controlling layer CCL. For example, the color filter layer CFL may be disposed directly on the light controlling layer CCL. In this case, the barrier layer BFL2 may not be provided.
The color filter layer CFL may include a light blocking part BM and filters CF1, CF2 and CF3. The color filter layer CFL may include a first filter CF1 transmitting second color light, a second filter CF2 transmitting third color light, and a third filter CF3 transmitting first color light. For example, the first filter CF1 may be a red filter, the second filter CF2 may be a green filter, and the third filter CF3 may be a blue filter. Each of the filters CF1, CF2 and CF3 may include a polymer photosensitive resin and a pigment or dye. The first filter CF1 may include a red pigment and/or dye, the second filter CF2 may include a green pigment and/or dye, and the third filter CF3 may include a blue pigment and/or dye. In some embodiments, embodiments of the present disclosure are not limited thereto, and the third filter CF3 may not include the pigment or dye. The third filter CF3 may include a polymer photosensitive resin and not include a pigment or dye. The third filter CF3 may be transparent. The third filter CF3 may be formed utilizing a transparent photosensitive resin.
In some embodiments, the first filter CF1 and/or the second filter CF2 may be yellow filters. The first filter CF1 and the second filter CF2 may be provided in one body without distinction.
The light blocking part BM may be a black matrix. The light blocking part BM may be formed by including an organic light blocking material or an inorganic light blocking material including a black pigment or black dye. The light blocking part BM may prevent or reduce light leakage phenomenon and divide the (e.g., act as) boundaries among adjacent filters CF1, CF2 and CF3. In some embodiments, the light blocking part BM may be formed as a blue filter.
Each of the first to third filters CF1, CF2 and CF3 may be disposed to respectively correspond to a red luminous area PXA-R, green luminous area PXA-G, and blue luminous area PXA-B.
On the color filter layer CFL, a base substrate BL may be disposed. The base substrate BL may provide a base surface on which the color filter layer CFL, the light controlling layer CCL, etc. are disposed. The base substrate BL may be a glass substrate, a metal substrate, a plastic substrate, etc. However, embodiments of the present disclosure are not limited thereto, and the base substrate BL may be an inorganic layer, an organic layer or a composite material layer. In some embodiments, the base substrate BL may not be provided.
For example, the luminescence device ED-BT included in the display apparatus DD-TD of an embodiment may be a luminescence device of a tandem structure including multiple emission layers.
In an embodiment shown in
A charge generating layer CGL1 and CGL2 may be disposed between neighboring light emitting structures OL-B1, OL-B2 and OL-B3. The charge generating layer CGL1 and CGL2 may include a p-type charge generating layer and/or an n-type charge generating layer.
Hereinafter, the present disclosure will be explained referring to embodiments and comparative embodiments. The embodiments are only illustrations to assist the understanding of the present disclosure, and the scope of the present disclosure is not limited thereto.
The amine compound according to embodiments of the present disclosure may be synthesized, for example, as follows. However, the synthetic method of the amine compound according to embodiments of the present disclosure is not limited to the embodiments.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 4,6-dibromodibenzofuran (25.00 g, 76.7 mmol), phenylboronic acid (10.29 g, 1.1 equiv, 84.4 mmol), K2CO3 (31.80 g, 3.0 equiv, 230.1 mmol), Pd(PPh3)4 (4.43 g, 0.05 eq, 3.8 mmol), and 540 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-1 (19.08 g, yield 77%).
Through FAB-MS measurement, mass number m/z=323 was observed as an ion peak, and Intermediate IM-1 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-1 (15.00 g, 46.4 mmol), Pd(dba)2 (0.80 g, 0.03 equiv, 1.4 mmol), NaOtBu (4.46 g, 1.0 equiv, 46.4 mmol), toluene (232 mL), 4-aminodibenzofuran (9.35 g, 1.1 equiv, 51.1 mmol) and tBu3P (0.94 g, 0.1 equiv, 4.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-2 (15.79 g, yield 80%).
Through FAB-MS measurement, mass number m/z=425 was observed as an ion peak, and Intermediate IM-2 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-2 (10.00 g, 23.5 mmol), Pd(dba)2 (0.41 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.52 g, 2.0 equiv, 47.0 mmol), toluene (118 mL), 2-(4-bromophenyl)naphthalene (7.32 g, 1.1 equiv, 25.9 mmol) and tBu3P (0.48 g, 0.1 equiv, 2.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound A2 of a solid (12.10 g, yield 82%).
Through FAB-MS measurement, mass number m/z=627 was observed as an ion peak, and Compound A2 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-1 (15.00 g, 46.4 mmol), Pd(dba)2 (0.80 g, 0.03 equiv, 1.4 mmol), NaOtBu (4.46 g, 1.0 equiv, 46.4 mmol), toluene (232 mL), 2-aminodibenzofuran (9.35 g, 1.1 equiv, 51.1 mmol) and tBu3P (0.94 g, 0.1 equiv, 4.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-3 (15.40 g, yield 78%).
Through FAB-MS measurement, mass number m/z=425 was observed as an ion peak, and Intermediate IM-3 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-3 (10.00 g, 23.5 mmol), Pd(dba)2 (0.41 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.52 g, 2.0 equiv, 47.0 mmol), toluene (118 mL), 9-(4-bromophenyl)phenanthrene (8.61 g, 1.1 equiv, 25.9 mmol) and tBu3P (0.48 g, 0.1 equiv, 2.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound A53 of a solid (12.43 g, yield 76%).
Through FAB-MS measurement, mass number m/z=677 was observed as an ion peak, and Compound A53 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-1 (15.00 g, 46.4 mmol), Pd(dba)2 (0.80 g, 0.03 equiv, 1.4 mmol), NaOtBu (4.46 g, 1.0 equiv, 46.4 mmol), toluene (232 mL), 3-aminodibenzothiophene (10.17 g, 1.1 equiv, 51.1 mmol) and tBu3P (0.94 g, 0.1 equiv, 4.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-4 (16.19 g, yield 79%).
Through FAB-MS measurement, mass number m/z=441 was observed as an ion peak, and Intermediate IM-4 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-4 (10.00 g, 22.6 mmol), Pd(dba)2 (0.39 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.35 g, 2.0 equiv, 45.3 mmol), toluene (113 mL), 4-bromo-1,1′:4′,1″-terphenyl (7.70 g, 1.1 equiv, 24.9 mmol) and tBu3P (0.46 g, 0.1 equiv, 2.3 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound B31 of a solid (12.59 g, yield 83%).
Through FAB-MS measurement, mass number m/z=669 was observed as an ion peak, and Compound B31 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-1 (15.00 g, 46.4 mmol), Pd(dba)2 (0.80 g, 0.03 equiv, 1.4 mmol), NaOtBu (4.46 g, 1.0 equiv, 46.4 mmol), toluene (232 mL), 1-aminodibenzothiophene (10.17 g, 1.1 equiv, 51.1 mmol) and tBu3P (0.94 g, 0.1 equiv, 4.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-5 (14.96 g, yield 73%).
Through FAB-MS measurement, mass number m/z=441 was observed as an ion peak, and Intermediate IM-5 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-5 (10.00 g, 22.6 mmol), Pd(dba)2 (0.39 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.35 g, 2.0 equiv, 45.3 mmol), toluene (113 mL), 2-bromo-6-phenylnaphthalene (7.05 g, 1.1 equiv, 24.9 mmol) and tBu3P (0.46 g, 0.1 equiv, 2.3 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound B88 of a solid (10.94 g, yield 75%).
Through FAB-MS measurement, mass number m/z=643 was observed as an ion peak, and Compound B88 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 4,6-dibromodibenzothiophene (25.00 g, 73.1 mmol), phenylboronic acid (9.80 g, 1.1 equiv, 80.4 mmol), K2CO3 (30.30 g, 3.0 equiv, 219.3 mmol), Pd(PPh3)4 (4.22 g, 0.05 eq, 3.7 mmol), and 512 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-6 (18.60 g, yield 75%).
Through FAB-MS measurement, mass number m/z=339 was observed as an ion peak, and Intermediate IM-6 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-6 (15.00 g, 44.2 mmol), Pd(dba)2 (0.76 g, 0.03 equiv, 1.3 mmol), NaOtBu (4.25 g, 1.0 equiv, 44.2 mmol), toluene (220 mL), 4-aminodibenzofuran (8.91 g, 1.1 equiv, 48.6 mmol) and tBu3P (0.89 g, 0.1 equiv, 4.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-7 (14.84 g, yield 76%).
Through FAB-MS measurement, mass number m/z=441 was observed as an ion peak, and Intermediate IM-7 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-7 (10.00 g, 22.6 mmol), Pd(dba)2 (0.39 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.35 g, 2.0 equiv, 45.3 mmol), toluene (113 mL), 3-bromodibenzofuran (6.16 g, 1.1 equiv, 24.9 mmol) and tBu3P (0.46 g, 0.1 equiv, 2.3 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound C19 of a solid (11.15 g, yield 81%).
Through FAB-MS measurement, mass number m/z=607 was observed as an ion peak, and Compound C19 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-6 (15.00 g, 44.2 mmol), Pd(dba)2 (0.76 g, 0.03 equiv, 1.3 mmol), NaOtBu (4.25 g, 1.0 equiv, 44.2 mmol), toluene (220 mL), 2-aminodibenzofuran (8.91 g, 1.1 equiv, 48.6 mmol) and tBu3P (0.89 g, 0.1 equiv, 4.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-8 (15.23 g, yield 78%).
Through FAB-MS measurement, mass number m/z=441 was observed as an ion peak, and Intermediate IM-8 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-8 (10.00 g, 22.6 mmol), Pd(dba)2 (0.39 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.35 g, 2.0 equiv, 45.3 mmol), toluene (113 mL), 3-(chlorophenyl)phenanthrene (7.19 g, 1.1 equiv, 24.9 mmol) and tBu3P (0.46 g, 0.1 equiv, 2.3 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound C55 of a solid (11.47 g, yield 73%).
Through FAB-MS measurement, mass number m/z=693 was observed as an ion peak, and Compound C55 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-6 (15.00 g, 44.2 mmol), Pd(dba)2 (0.76 g, 0.03 equiv, 1.3 mmol), NaOtBu (4.25 g, 1.0 equiv, 44.2 mmol), toluene (220 mL), 2-aminodibenzothiophene (9.69 g, 1.1 equiv, 48.6 mmol) and tBu3P (0.89 g, 0.1 equiv, 4.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-9 (15.38 g, yield 76%).
Through FAB-MS measurement, mass number m/z=457 was observed as an ion peak, and Intermediate IM-9 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-9 (10.00 g, 21.9 mmol), Pd(dba)2 (0.38 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.20 g, 2.0 equiv, 43.7 mmol), toluene (110 mL), 2-(2-bromophenyl)naphthalene (6.81 g, 1.1 equiv, 24.0 mmol) and tBu3P (0.44 g, 0.1 equiv, 2.2 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound D40 of a solid (9.95 g, yield 69%).
Through FAB-MS measurement, mass number m/z=659 was observed as an ion peak, and Compound D40 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-6 (15.00 g, 44.2 mmol), Pd(dba)2 (0.76 g, 0.03 equiv, 1.3 mmol), NaOtBu (4.25 g, 1.0 equiv, 44.2 mmol), toluene (220 mL), 1-aminodibenzothiophene (9.69 g, 1.1 equiv, 48.6 mmol) and tBu3P (0.89 g, 0.1 equiv, 4.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-10 (15.17 g, yield 75%).
Through FAB-MS measurement, mass number m/z=457 was observed as an ion peak, and Intermediate IM-10 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-10 (10.00 g, 21.9 mmol), Pd(dba)2 (0.38 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.20 g, 2.0 equiv, 43.7 mmol), toluene (110 mL), 2-(4-chlorophenyl)phenanthrene (6.94 g, 1.1 equiv, 24.0 mmol) and tBu3P (0.44 g, 0.1 equiv, 2.2 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound D54 of a solid (12.41 g, yield 80%).
Through FAB-MS measurement, mass number m/z=709 was observed as an ion peak, and Compound D54 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 4-bromodibenzofuran (20.00 g, 80.9 mmol), (3-aminophenyl)boronic acid (12.19 g, 1.1 equiv, 89.0 mmol), K2CO3 (33.56 g, 3.0 equiv, 242.8 mmol), Pd(PPh3)4 (4.68 g, 0.05 eq, 4.0 mmol), and 566 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-11 (15.74 g, yield 75%).
Through FAB-MS measurement, mass number m/z=259 was observed as an ion peak, and Intermediate IM-11 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-11 (10.00 g, 38.6 mmol), Pd(dba)2 (0.67 g, 0.03 equiv, 1.2 mmol), NaOtBu (3.71 g, 1.0 equiv, 38.6 mmol), toluene (192 mL), IM-1 (13.71 g, 1.1 equiv, 42.4 mmol) and tBu3P (0.78 g, 0.1 equiv, 3.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-12 (14.31 g, yield 74%).
Through FAB-MS measurement, mass number m/z=501 was observed as an ion peak, and Intermediate IM-12 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-12 (10.00 g, 19.9 mmol), Pd(dba)2 (0.34 g, 0.03 equiv, 0.6 mmol), NaOtBu (3.83 g, 2.0 equiv, 39.9 mmol), toluene (113 mL), 1-(4-bromophenyl)naphthalene (6.21 g, 1.1 equiv, 21.9 mmol) and tBu3P (0.40 g, 0.1 equiv, 2.0 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound E19 of a solid (11.23 g, yield 80%).
Through FAB-MS measurement, mass number m/z=703 was observed as an ion peak, and Compound E19 was identified. 10. Synthesis of Compound E113
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 2-bromodibenzofuran (20.00 g, 80.9 mmol), (4-aminophenyl)boronic acid (12.19 g, 1.1 equiv, 89.0 mmol), K2CO3 (33.56 g, 3.0 equiv, 242.8 mmol), Pd(PPh3)4 (4.68 g, 0.05 eq, 4.0 mmol), and 566 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-13 (16.58 g, yield 79%).
Through FAB-MS measurement, mass number m/z=259 was observed as an ion peak, and Intermediate IM-13 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-14 (10.00 g, 38.6 mmol), Pd(dba)2 (0.67 g, 0.03 equiv, 1.2 mmol), NaOtBu (3.71 g, 1.0 equiv, 38.6 mmol), toluene (192 mL), IM-1 (13.71 g, 1.1 equiv, 42.4 mmol) and tBu3P (0.78 g, 0.1 equiv, 3.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-14 (14.89 g, yield 77%).
Through FAB-MS measurement, mass number m/z=501 was observed as an ion peak, and Intermediate IM-14 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-14 (10.00 g, 19.9 mmol), Pd(dba)2 (0.34 g, 0.03 equiv, 0.6 mmol), NaOtBu (3.83 g, 2.0 equiv, 39.9 mmol), toluene (113 mL), 4-bromodibenzothiophene (5.77 g, 1.1 equiv, 21.9 mmol) and tBu3P (0.40 g, 0.1 equiv, 2.0 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound E113 of a solid (10.19 g, yield 74%).
Through FAB-MS measurement, mass number m/z=683 was observed as an ion peak, and Compound E113 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, dibenzothiophen-4-ylboronic acid (10.00 g, 43.8 mmol), 4′-bromo-[1,1′-biphenyl]-4-amine (11.96 g, 1.1 equiv, 48.2 mmol), K2CO3 (18.18 g, 3.0 equiv, 131.5 mmol), Pd(PPh3)4 (2.53 g, 0.05 eq, 2.2 mmol), and 307 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-15 (12.02 g, yield 78%).
Through FAB-MS measurement, mass number m/z=351 was observed as an ion peak, and Intermediate IM-15 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-15 (10.00 g, 28.5 mmol), Pd(dba)2 (0.49 g, 0.03 equiv, 0.9 mmol), NaOtBu (2.73 g, 1.0 equiv, 28.5 mmol), toluene (142 mL), IM-1 (10.11 g, 1.1 equiv, 31.3 mmol) and tBu3P (0.58 g, 0.1 equiv, 2.8 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-16 (12.33 g, yield 73%).
Through FAB-MS measurement, mass number m/z=593 was observed as an ion peak, and Intermediate IM-16 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-16 (10.00 g, 16.8 mmol), Pd(dba)2 (0.29 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.24 g, 2.0 equiv, 33.7 mmol), toluene (84 mL), 1-(4-bromophenyl)naphthalene (5.25 g, 1.1 equiv, 18.5 mmol) and tBu3P (0.34 g, 0.1 equiv, 1.7 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound F22 of a solid (10.32 g, yield 74%).
Through FAB-MS measurement, mass number m/z=796 was observed as an ion peak, and Compound F22 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 1-bromodibenzothiophene (20.00 g, 76.0 mmol), (4-aminophenyl)boronic acid (11.45 g, 1.1 equiv, 83.6 mmol), K2CO3 (31.51 g, 3.0 equiv, 228.0 mmol), Pd(PPh3)4 (4.39 g, 0.05 eq, 3.8 mmol), and 532 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-17 (15.49 g, yield 74%).
Through FAB-MS measurement, mass number m/z=275 was observed as an ion peak, and Intermediate IM-17 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-17 (10.00 g, 36.3 mmol), Pd(dba)2 (0.63 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.49 g, 1.0 equiv, 36.3 mmol), toluene (182 mL), IM-1 (12.91 g, 1.1 equiv, 39.9 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-18 (13.53 g, yield 72%).
Through FAB-MS measurement, mass number m/z=517 was observed as an ion peak, and Intermediate IM-18 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-18 (10.00 g, 19.3 mmol), Pd(dba)2 (0.33 g, 0.03 equiv, 0.6 mmol), NaOtBu (3.71 g, 2.0 equiv, 38.6 mmol), toluene (97 mL), 4-bromobiphenyl (4.95 g, 1.1 equiv, 21.2 mmol) and tBu3P (0.39 g, 0.1 equiv, 1.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound F129 of a solid (10.61 g, yield 82%).
Through FAB-MS measurement, mass number m/z=669 was observed as an ion peak, and Compound F129 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, IM-1 (20.00 g, 61.9 mmol), (4-aminophenyl)boronic acid (9.32 g, 1.1 equiv, 68.1 mmol), K2CO3 (25.66 g, 3.0 equiv, 185.6 mmol), Pd(PPh3)4 (3.58 g, 0.05 eq, 3.1 mmol), and 434 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-19 (15.15 g, yield 73%).
Through FAB-MS measurement, mass number m/z=351 was observed as an ion peak, and Intermediate IM-19 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-19 (10.00 g, 29.8 mmol), Pd(dba)2 (0.51 g, 0.03 equiv, 0.9 mmol), NaOtBu (2.87 g, 1.0 equiv, 29.8 mmol), toluene (150 mL), IM-6 (11.13 g, 1.1 equiv, 32.8 mmol) and tBu3P (0.60 g, 0.1 equiv, 3.0 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-20 (12.39 g, yield 70%).
Through FAB-MS measurement, mass number m/z=593 was observed as an ion peak, and Intermediate IM-20 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-20 (10.00 g, 16.8 mmol), Pd(dba)2 (0.29 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.24 g, 2.0 equiv, 33.7 mmol), toluene (84 mL), 4-bromodibenzofuran (4.58 g, 1.1 equiv, 18.5 mmol) and tBu3P (0.34 g, 0.1 equiv, 1.7 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound G28 of a solid (10.11 g, yield 79%).
Through FAB-MS measurement, mass number m/z=759 was observed as an ion peak, and Compound G28 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 3-bromodibenzofuran (20.00 g, 80.9 mmol), (4-aminophenyl)boronic acid (12.19 g, 1.1 equiv, 89.0 mmol), K2CO3 (33.56 g, 3.0 equiv, 242.8 mmol), Pd(PPh3)4 (4.68 g, 0.05 eq, 4.0 mmol), and 566 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-21 (16.79 g, yield 80%).
Through FAB-MS measurement, mass number m/z=259 was observed as an ion peak, and Intermediate IM-21 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-21 (10.00 g, 38.6 mmol), Pd(dba)2 (0.67 g, 0.03 equiv, 1.2 mmol), NaOtBu (3.71 g, 1.0 equiv, 38.6 mmol), toluene (192 mL), IM-6 (14.39 g, 1.1 equiv, 42.4 mmol) and tBu3P (0.78 g, 0.1 equiv, 3.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-22 (14.77 g, yield 74%).
Through FAB-MS measurement, mass number m/z=517 was observed as an ion peak, and Intermediate IM-22 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-22 (10.00 g, 19.3 mmol), Pd(dba)2 (0.33 g, 0.03 equiv, 0.6 mmol), NaOtBu (3.71 g, 2.0 equiv, 38.6 mmol), toluene (97 mL), 2-bromonaphthalene (4.40 g, 1.1 equiv, 21.2 mmol) and tBu3P (0.39 g, 0.1 equiv, 1.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound G51 of a solid (10.07 g, yield 81%).
Through FAB-MS measurement, mass number m/z=643 was observed as an ion peak, and Compound G51 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 4-bromodibenzothiophene (20.00 g, 76.0 mmol), (4-aminophenyl)boronic acid (11.45 g, 1.1 equiv, 83.6 mmol), K2CO3 (31.51 g, 3.0 equiv, 228.0 mmol), Pd(PPh3)4 (4.39 g, 0.05 eq, 3.8 mmol), and 532 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-23 (16.32 g, yield 78%).
Through FAB-MS measurement, mass number m/z=275 was observed as an ion peak, and Intermediate IM-23 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-23 (10.00 g, 36.3 mmol), Pd(dba)2 (0.63 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.49 g, 1.0 equiv, 36.3 mmol), toluene (182 mL), IM-6 (13.55 g, 1.1 equiv, 39.9 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-24 (14.73 g, yield 76%).
Through FAB-MS measurement, mass number m/z=533 was observed as an ion peak, and Intermediate IM-24 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-24 (10.00 g, 18.7 mmol), Pd(dba)2 (0.32 g, 0.03 equiv, 0.6 mmol), NaOtBu (3.60 g, 2.0 equiv, 37.4 mmol), toluene (94 mL), 1-(4-bromophenyl)naphthalene (5.84 g, 1.1 equiv, 20.6 mmol) and tBu3P (0.38 g, 0.1 equiv, 1.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound H1 of a solid (10.89 g, yield 79%).
Through FAB-MS measurement, mass number m/z=735 was observed as an ion peak, and Compound H1 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 2-bromodibenzothiophene (20.00 g, 76.0 mmol), (4-aminophenyl)boronic acid (11.45 g, 1.1 equiv, 83.6 mmol), K2CO3 (31.51 g, 3.0 equiv, 228.0 mmol), Pd(PPh3)4 (4.39 g, 0.05 eq, 3.8 mmol), and 532 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-25 (15.70 g, yield 75%).
Through FAB-MS measurement, mass number m/z=275 was observed as an ion peak, and Intermediate IM-25 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-25 (10.00 g, 36.3 mmol), Pd(dba)2 (0.63 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.49 g, 1.0 equiv, 36.3 mmol), toluene (182 mL), IM-6 (13.55 g, 1.1 equiv, 39.9 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-26 (15.31 g, yield 79%).
Through FAB-MS measurement, mass number m/z=533 was observed as an ion peak, and Intermediate IM-26 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-26 (10.00 g, 18.7 mmol), Pd(dba)2 (0.32 g, 0.03 equiv, 0.6 mmol), NaOtBu (3.60 g, 2.0 equiv, 37.4 mmol), toluene (94 mL), 4-bromo-1,1′:2′,1″-terphenyl (6.37 g, 1.1 equiv, 20.6 mmol) and tBu3P (0.38 g, 0.1 equiv, 1.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound H88 of a solid (10.14 g, yield 71%).
Through FAB-MS measurement, mass number m/z=762 was observed as an ion peak, and Compound H88 was identified.
Under an Ar atmosphere, to a 2000 mL, three-neck flask, 2-bromo-1-iodo-3-methoxybenzene (50.00 g, 159.8 mmol), phenylboronic acid (21.43 g, 1.1 equiv, 175.8 mmol), K2CO3 (66.25 g, 3.0 equiv, 479.3 mmol), Pd(PPh3)4 (9.23 g, 0.05 eq, 8.0 mmol), and 1118 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-27 (32.37 g, yield 77%).
Through FAB-MS measurement, mass number m/z=263 was observed as an ion peak, and Intermediate IM-27 was identified.
Under an Ar atmosphere, to a 2000 mL, three-neck flask, IM-27 (30.00 g, 114.0 mmol), (3-chloro-2-fluorophenyl)boronic acid (21.87 g, 1.1 equiv, 125.4 mmol), K2CO3 (47.27 g, 3.0 equiv, 342.0 mmol), Pd(PPh3)4 (6.59 g, 0.05 eq, 5.7 mmol), and 798 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-28 (28.57 g, yield 80%).
Through FAB-MS measurement, mass number m/z=312 was observed as an ion peak, and Intermediate IM-28 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, IM-28 (25.00 g, 79.9 mmol), CH2Cl2 (266 mL) and a CH2Cl2 solution of 1 M BBr3 (240 mL, 3.0 equiv, 240 mmol) were added in order, and stirred at room temperature for about 24 hours. The reaction solution was neutralized with a saturated NaHCO3 aqueous solution and extracted with CH2Cl2. An organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-29 (20.30 g, yield 85%).
Through FAB-MS measurement, mass number m/z=298 was observed as an ion peak, and Intermediate IM-29 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-29 (18.00 g, 60.3 mmol), DMF (302 mL) and K2CO3 (33.31 g, 4 equiv, 241.0 mmol) were added in order, and heated to about 140° C. and stirred. After cooling to room temperature, H2O was added to the reaction solution, and an organic layer was extracted with toluene, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-30 (13.77 g, yield 82%).
Through FAB-MS measurement, mass number m/z=278 was observed as an ion peak, and Intermediate IM-30 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-30 (10.00 g, 35.9 mmol), Pd(dba)2 (0.62 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.45 g, 1.0 equiv, 35.9 mmol), toluene (180 mL), 4-(naphthalen-2-yl)aniline (8.65 g, 1.1 equiv, 39.5 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-31 (12.42 g, yield 75%).
Through FAB-MS measurement, mass number m/z=461 was observed as an ion peak, and Intermediate IM-31 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-31 (8.00 g, 17.3 mmol), Pd(dba)2 (0.30 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.33 g, 2.0 equiv, 34.7 mmol), toluene (87 mL), 1-(4-bromophenyl)naphthalene (5.40 g, 1.1 equiv, 19.1 mmol) and tBu3P (0.35 g, 0.1 equiv, 1.7 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound I3 of a solid (9.20 g, yield 80%).
Through FAB-MS measurement, mass number m/z=663 was observed as an ion peak, and Compound I3 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-30 (10.00 g, 35.9 mmol), Pd(dba)2 (0.62 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.45 g, 1.0 equiv, 35.9 mmol), toluene (180 mL), [1,1′:3′,1″-terphenyl]-4-amine (9.68 g, 1.1 equiv, 39.5 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-32 (12.59 g, yield 72%).
Through FAB-MS measurement, mass number m/z=487 was observed as an ion peak, and Intermediate IM-32 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-32 (8.00 g, 16.4 mmol), Pd(dba)2 (0.28 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.15 g, 2.0 equiv, 32.8 mmol), toluene (82 mL), 4-chloro-1,1′:3′,1″-terphenyl (4.78 g, 1.1 equiv, 18.0 mmol) and tBu3P (0.33 g, 0.1 equiv, 1.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound I10 of a solid (8.93 g, yield 76%).
Through FAB-MS measurement, mass number m/z=715 was observed as an ion peak, and Compound I10 was identified. 19. Synthesis of Compound J15
Under an Ar atmosphere, to a 2000 mL, three-neck flask, 2-bromo-4-iodo-1-methoxybenzene (50.00 g, 159.8 mmol), phenylboronic acid (21.43 g, 1.1 equiv, 175.8 mmol), K2CO3 (66.25 g, 3.0 equiv, 479.3 mmol), Pd(PPh3)4 (9.23 g, 0.05 eq, 8.0 mmol), and 1118 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-33 (32.79 g, yield 78%).
Through FAB-MS measurement, mass number m/z=263 was observed as an ion peak, and Intermediate IM-33 was identified.
Under an Ar atmosphere, to a 2000 mL, three-neck flask, IM-33 (30.00 g, 114.0 mmol), (3-chloro-2-fluorophenyl)boronic acid (21.87 g, 1.1 equiv, 125.4 mmol), K2CO3 (47.27 g, 3.0 equiv, 342.0 mmol), Pd(PPh3)4 (6.59 g, 0.05 eq, 5.7 mmol), and 798 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-34 (29.60 g, yield 83%).
Through FAB-MS measurement, mass number m/z=312 was observed as an ion peak, and Intermediate IM-34 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, IM-34 (25.00 g, 79.9 mmol), CH2Cl2 (266 mL) and a CH2Cl2 solution of 1 M BBr3 (240 mL, 3.0 equiv, 240 mmol) were added in order, and stirred at room temperature for about 24 hours. The reaction solution was neutralized with a saturated NaHCO3 aqueous solution and extracted with CH2Cl2. An organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-35 (20.06 g, yield 84%).
Through FAB-MS measurement, mass number m/z=298 was observed as an ion peak, and Intermediate IM-35 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-35 (18.00 g, 60.3 mmol), DMF (302 mL) and K2CO3 (33.31 g, 4 equiv, 241.0 mmol) were added in order, and heated to about 140° C. and stirred. After cooling to room temperature, H2O was added to the reaction solution, and an organic layer was extracted with toluene, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-36 (13.44 g, yield 80%).
Through FAB-MS measurement, mass number m/z=278 was observed as an ion peak, and Intermediate IM-36 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-36 (10.00 g, 35.9 mmol), Pd(dba)2 (0.62 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.45 g, 1.0 equiv, 35.9 mmol), toluene (180 mL), 4-(phenanthren-2-yl)aniline (10.63 g, 1.1 equiv, 39.5 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-37 (14.32 g, yield 78%).
Through FAB-MS measurement, mass number m/z=511 was observed as an ion peak, and Intermediate IM-37 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-37 (8.00 g, 15.6 mmol), Pd(dba)2 (0.27 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.01 g, 2.0 equiv, 31.3 mmol), toluene (78 mL), 3-(4-chlorophenyl)phenanthrene (5.21 g, 1.1 equiv, 17.2 mmol) and tBu3P (0.32 g, 0.1 equiv, 1.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound J15 of a solid (10.40 g, yield 83%).
Through FAB-MS measurement, mass number m/z=763 was observed as an ion peak, and Compound J15 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-36 (10.00 g, 35.9 mmol), Pd(dba)2 (0.62 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.45 g, 1.0 equiv, 35.9 mmol), toluene (180 mL), naphthalen-2-amine (5.34 g, 1.1 equiv, 39.5 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-38 (10.72 g, yield 82%).
Through FAB-MS measurement, mass number m/z=385 was observed as an ion peak, and Intermediate IM-38 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-38 (8.00 g, 20.8 mmol), Pd(dba)2 (0.36 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.99 g, 2.0 equiv, 41.5 mmol), toluene (108 mL), 1-[4′-chloro-(1,1′-biphenyl)-4-yl]naphthalene (7.19 g, 1.1 equiv, 22.8 mmol) and tBu3P (0.42 g, 0.1 equiv, 2.1 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound J18 of a solid (11.71 g, yield 85%).
Through FAB-MS measurement, mass number m/z=663 was observed as an ion peak, and Compound J18 was identified.
Under an Ar atmosphere, to a 2000 mL, three-neck flask, 1-bromo-4-iodo-2-methoxybenzene (50.00 g, 159.8 mmol), phenylboronic acid (21.43 g, 1.1 equiv, 175.8 mmol), K2CO3 (66.25 g, 3.0 equiv, 479.3 mmol), Pd(PPh3)4 (9.23 g, 0.05 eq, 8.0 mmol), and 1118 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-39 (33.63 g, yield 80%).
Through FAB-MS measurement, mass number m/z=263 was observed as an ion peak, and Intermediate IM-39 was identified.
Under an Ar atmosphere, to a 2000 mL, three-neck flask, IM-39 (30.00 g, 114.0 mmol), (3-chloro-2-fluorophenyl)boronic acid (21.87 g, 1.1 equiv, 125.4 mmol), K2CO3 (47.27 g, 3.0 equiv, 342.0 mmol), Pd(PPh3)4 (6.59 g, 0.05 eq, 5.7 mmol), and 798 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-40 (27.10 g, yield 76%).
Through FAB-MS measurement, mass number m/z=312 was observed as an ion peak, and Intermediate IM-40 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, IM-40 (25.00 g, 79.9 mmol), CH2Cl2 (266 mL) and a CH2Cl2 solution of 1 M BBr3 (240 mL, 3.0 equiv, 240 mmol) were added in order, and stirred at room temperature for about 24 hours. The reaction solution was neutralized with a saturated NaHCO3 aqueous solution and extracted with CH2Cl2. An organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-41 (19.58 g, yield 82%).
Through FAB-MS measurement, mass number m/z=298 was observed as an ion peak, and Intermediate IM-41 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-41 (18.00 g, 60.3 mmol), DMF (302 mL) and K2CO3 (33.31 g, 4 equiv, 241.0 mmol) were added in order, and heated to about 140° C. and stirred. After cooling to room temperature, H2O was added to the reaction solution, and an organic layer was extracted with toluene, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-42 (13.10 g, yield 78%).
Through FAB-MS measurement, mass number m/z=278 was observed as an ion peak, and Intermediate IM-42 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-42 (10.00 g, 35.9 mmol), Pd(dba)2 (0.62 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.45 g, 1.0 equiv, 35.9 mmol), toluene (180 mL), 4-phenylnaphthalen-1-amine (8.65 g, 1.1 equiv, 39.5 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-43 (12.75 g, yield 77%).
Through FAB-MS measurement, mass number m/z=461 was observed as an ion peak, and Intermediate IM-43 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-43 (8.00 g, 17.3 mmol), Pd(dba)2 (0.30 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.33 g, 2.0 equiv, 34.7 mmol), toluene (87 mL), 2-(4-chlorophenyl)phenanthrene (5.51 g, 1.1 equiv, 19.1 mmol) and tBu3P (0.35 g, 0.1 equiv, 1.7 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound K6 of a solid (9.77 g, yield 79%).
Through FAB-MS measurement, mass number m/z=713 was observed as an ion peak, and Compound K6 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, [1,1′-biphenyl]-2-ol (20.00 g, 170.2 mmol), 2-bromo-1-chloro-3-fluorobenzene (49.22 g, 2 equiv, 235.0 mmol), DMF (588 mL) and K2CO3 (65.0 g, 4 equiv, 470.0 mmol) were added in order, and heated to about 140° C. and stirred. After cooling to room temperature, H2O was added to the reaction solution, and an organic layer was extracted with toluene, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-44 (32.96 g, yield 78%).
Through FAB-MS measurement, mass number m/z=359 was observed as an ion peak, and Intermediate IM-44 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-44 (25.00 g, 69.5 mmol), Pd(OAc)2 (0.78 g, 0.05 equiv, 3.5 mmol), K2CO3 (14.41 g, 1.5 equiv, 104.3 mmol), N,N-dimethylacetamide (DMA, 278 mL) and PPh3 (1.82 g, 0.1 equiv, 7.0 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-45 (13.37 g, yield 69%).
Through FAB-MS measurement, mass number m/z=278 was observed as an ion peak, and Intermediate IM-45 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-45 (8.00 g, 28.7 mmol), Pd(dba)2 (0.50 g, 0.03 equiv, 0.9 mmol), NaOtBu (5.52 g, 2.0 equiv, 57.4 mmol), toluene (144 mL), bis(4-biphenylyl)amine (10.15 g, 1.1 equiv, 31.6 mmol) and tBu3P (0.58 g, 0.1 equiv, 2.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound L1 of a solid (12.94 g, yield 80%).
Through FAB-MS measurement, mass number m/z=563 was observed as an ion peak, and Compound L1 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, [1,1′-biphenyl]-3-ol (20.00 g, 170.2 mmol), 2-bromo-1-chloro-3-fluorobenzene (49.22 g, 2 equiv, 235.0 mmol), DMF 588 mL and K2CO3 65.0 g (4 equiv, 470.0 mmol) were added in order, and heated to about 140° C. and stirred. After cooling to room temperature, H2O was added to the reaction solution, and an organic layer was extracted with toluene, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-46 (33.81 g, yield 80%).
Through FAB-MS measurement, mass number m/z=359 was observed as an ion peak, and Intermediate IM-47 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, IM-46 (25.00 g, 69.5 mmol), Pd(OAc)2 (0.78 g, 0.05 equiv, 3.5 mmol), K2CO3 (14.41 g, 1.5 equiv, 104.3 mmol), N,N-dimethylacetamide (DMA, 278 mL) and PPh3 (1.82 g, 0.1 equiv, 7.0 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-47 (12.59 g, yield 65%).
Through FAB-MS measurement, mass number m/z=278 was observed as an ion peak, and Intermediate IM-47 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-47 (10.00 g, 35.9 mmol), Pd(dba)2 (0.62 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.45 g, 1.0 equiv, 35.9 mmol), toluene (180 mL), 4-(phenanthren-3-yl)aniline (10.63 g, 1.1 equiv, 39.5 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-48 (14.68 g, yield 80%).
Through FAB-MS measurement, mass number m/z=511 was observed as an ion peak, and Intermediate IM-48 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-48 (8.00 g, 15.6 mmol), Pd(dba)2 (0.27 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.01 g, 2.0 equiv, 31.3 mmol), toluene (78 mL), 4-bromobiphenyl (4.01 g, 1.1 equiv, 17.2 mmol) and tBu3P (0.32 g, 0.1 equiv, 1.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound M5 of a solid (8.30 g, yield 80%).
Through FAB-MS measurement, mass number m/z=663 was observed as an ion peak, and Compound M5 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-47 (10.00 g, 35.9 mmol), Pd(dba)2 (0.62 g, 0.03 equiv, 1.1 mmol), NaOtBu (3.45 g, 1.0 equiv, 35.9 mmol), toluene (180 mL), 4-(phenanthren-2-yl)aniline (10.63 g, 1.1 equiv, 39.5 mmol) and tBu3P (0.73 g, 0.1 equiv, 3.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-49 (13.58 g, yield 74%).
Through FAB-MS measurement, mass number m/z=511 was observed as an ion peak, and Intermediate IM-49 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-49 (8.00 g, 15.6 mmol), Pd(dba)2 (0.27 g, 0.03 equiv, 0.5 mmol), NaOtBu (3.01 g, 2.0 equiv, 31.3 mmol), toluene (78 mL), 2-bromodibenzothiophene (4.53 g, 1.1 equiv, 17.2 mmol) and tBu3P (0.32 g, 0.1 equiv, 1.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound M20 of a solid (8.57 g, yield 79%).
Through FAB-MS measurement, mass number m/z=693 was observed as an ion peak, and Compound M20 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, [1,1′-biphenyl]-4-ol (20.00 g, 170.2 mmol), 2-bromo-1-chloro-3-fluorobenzene (49.22 g, 2 equiv, 235.0 mmol), DMF (588 mL) and K2CO3 (65.0 g, 4 equiv, 470.0 mmol) were added in order, and heated to about 140° C. and stirred. After cooling to room temperature, H2O was added to the reaction solution, and an organic layer was extracted with toluene, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-50 (33.81 g, yield 80%).
Through FAB-MS measurement, mass number m/z=359 was observed as an ion peak, and Intermediate IM-50 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-50 (25.00 g, 69.5 mmol), Pd(OAc)2 (0.78 g, 0.05 equiv, 3.5 mmol), K2CO3 (14.41 g, 1.5 equiv, 104.3 mmol), N,N-dimethylacetamide (DMA, 278 mL) and PPh3 (1.82 g, 0.1 equiv, 7.0 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-51 (14.34 g, yield 74%).
Through FAB-MS measurement, mass number m/z=278 was observed as an ion peak, and Intermediate IM-51 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-51 (8.00 g, 28.7 mmol), Pd(dba)2 (0.50 g, 0.03 equiv, 0.9 mmol), NaOtBu (5.52 g, 2.0 equiv, 57.4 mmol), toluene (144 mL), bis[4-(naphthalene-2-yl)phenyl]amine (13.31 g, 1.1 equiv, 31.6 mmol) and tBu3P (0.58 g, 0.1 equiv, 2.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound N4 of a solid (16.38 g, yield 86%).
Through FAB-MS measurement, mass number m/z=663 was observed as an ion peak, and Compound N4 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, [1,1′-biphenyl]-4-thiol (20.00 g, 107.4 mmol), 2-bromo-1-chloro-3-fluorobenzene (44.98 g, 2 equiv, 214.7 mmol), DMF (537 mL) and K2CO3 (59.36 g, 4 equiv, 429.5 mmol) were added in order, and heated to about 140° C. and stirred. After cooling to room temperature, H2O was added to the reaction solution, and an organic layer was extracted with toluene, washed with a saturated saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-52 (33.08 g, yield 82%).
Through FAB-MS measurement, mass number m/z=375 was observed as an ion peak, and Intermediate IM-52 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-52 (25.00 g, 66.5 mmol), Pd(OAc)2 (0.74 g, 0.05 equiv, 3.3 mmol), K2CO3 (13.79 g, 1.5 equiv, 99.8 mmol), N,N-dimethylacetamide (DMA, 266 mL) and PPh3 (1.74 g, 0.1 equiv, 6.7 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-53 (14.71 g, yield 75%).
Through FAB-MS measurement, mass number m/z=294 was observed as an ion peak, and Intermediate IM-53 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-53 (10.00 g, 33.9 mmol), Pd(dba)2 (0.58 g, 0.03 equiv, 1.0 mmol), NaOtBu (3.26 g, 1.0 equiv, 33.9 mmol), toluene (170 mL), 4-(dibenzofuran-4-yl)aniline (9.68 g, 1.1 equiv, 37.3 mmol) and tBu3P (0.69 g, 0.1 equiv, 3.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-54 (13.52 g, yield 77%).
Through FAB-MS measurement, mass number m/z=517 was observed as an ion peak, and Intermediate IM-54 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-54 (8.00 g, 15.5 mmol), Pd(dba)2 (0.27 g, 0.03 equiv, 0.5 mmol), NaOtBu (2.97 g, 2.0 equiv, 30.9 mmol), toluene (78 mL), 4-(4-bromophenyl)dibenzofuran (5.49 g, 1.1 equiv, 17.0 mmol) and tBu3P (0.31 g, 0.1 equiv, 1.5 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound N36 of a solid (9.51 g, yield 81%).
Through FAB-MS measurement, mass number m/z=759 was observed as an ion peak, and Compound N36 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-1 (15.00 g, 46.4 mmol), Pd(dba)2 (0.80 g, 0.03 equiv, 1.4 mmol), NaOtBu (4.46 g, 1.0 equiv, 46.4 mmol), toluene (232 mL), 4-(naphthalen-1-yl)aniline (11.20 g, 1.1 equiv, 51.1 mmol) and tBu3P (0.94 g, 0.1 equiv, 4.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-55 (16.07 g, yield 75%).
Through FAB-MS measurement, mass number m/z=461 was observed as an ion peak, and Intermediate IM-55 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-55 (10.00 g, 21.7 mmol), Pd(dba)2 (0.37 g, 0.03 equiv, 0.6 mmol), NaOtBu (4.16 g, 2.0 equiv, 43.3 mmol), toluene (108 mL), 4-bromo-1-phenyldibenzofuran (7.70 g, 1.1 equiv, 23.8 mmol) and tBu3P (0.44 g, 0.1 equiv, 2.2 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound A106 of a solid (11.74 g, yield 77%).
Through FAB-MS measurement, mass number m/z=703 was observed as an ion peak, and Compound A106 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-1 (15.00 g, 46.4 mmol), Pd(dba)2 (0.80 g, 0.03 equiv, 1.4 mmol), NaOtBu (4.46 g, 1.0 equiv, 46.4 mmol), toluene (232 mL), [1,1′:4′,1″-terphenyl]-4-amine (12.52 g, 1.1 equiv, 51.1 mmol) and tBu3P (0.94 g, 0.1 equiv, 4.6 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-56 (17.65 g, yield 78%).
Through FAB-MS measurement, mass number m/z=487 was observed as an ion peak, and Intermediate IM-56 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-56 (10.00 g, 20.5 mmol), Pd(dba)2 (0.35 g, 0.03 equiv, 0.6 mmol), NaOtBu (3.94 g, 2.0 equiv, 41.0 mmol), toluene (108 mL), 4-bromo-2-phenyldibenzofuran (7.29 g, 1.1 equiv, 22.6 mmol) and tBu3P (0.41 g, 0.1 equiv, 2.1 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound A107 of a solid (11.38 g, yield 76%).
Through FAB-MS measurement, mass number m/z=729 was observed as an ion peak, and Compound A107 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, 1,4-dibromonaphthalene (25.00 g, 87.4 mmol), (phenyl-d5)boronic acid (12.21 g, 1.1 equiv, 96.2 mmol), K2CO3 (36.25 g, 3.0 equiv, 262.3 mmol), Pd(PPh3)4 (5.05 g, 0.05 eq, 4.4 mmol) and 612 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-57 (18.64 g, yield 74%).
Through FAB-MS measurement, mass number m/z=288 was observed as an ion peak, and Intermediate IM-57 was identified.
Under an Ar atmosphere, to a 1000 mL, three-neck flask, IM-57 (15.00 g, 52.0 mmol), 4-chlorophenylboronic acid (8.95 g, 1.1 equiv, 57.3 mmol), K2CO3 (21.58 g, 3.0 equiv, 156.1 mmol), Pd(PPh3)4 (3.00 g, 0.05 eq, 2.6 mmol) and 364 mL of a mixture solution of toluene/EtOH/H2O (4/2/1) were added in order were added in order, and heated to about 80° C. and stirred. After cooling to room temperature, the reaction solution was extracted with toluene. An aqueous layer was removed, and an organic layer was washed with a saturated saline solution and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-58 (12.49 g, yield 75%).
Through FAB-MS measurement, mass number m/z=319 was observed as an ion peak, and Intermediate IM-58 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-2 (10.00 g, 23.5 mmol), Pd(dba)2 (0.41 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.52 g, 2.0 equiv, 47.0 mmol), toluene (118 mL), IM-58 (8.27 g, 1.1 equiv, 25.9 mmol) and tBu3P (0.48 g, 0.1 equiv, 2.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound A17 of a solid (13.16 g, yield 79%).
Through FAB-MS measurement, mass number m/z=708 was observed as an ion peak, and Compound A17 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-36 (15.00 g, 53.8 mmol), Pd(dba)2 (0.93 g, 0.03 equiv, 1.6 mmol), NaOtBu (5.17 g, 1.0 equiv, 53.8 mmol), toluene (269 mL), 3-aminodibenzothiophene (11.80 g, 1.1 equiv, 59.2 mmol) and tBu3P (1.09 g, 0.1 equiv, 5.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. Organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-59 (17.35 g, yield 73%).
Through FAB-MS measurement, mass number m/z=441 was observed as an ion peak, and Intermediate IM-59 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-59 (10.00 g, 22.6 mmol), Pd(dba)2 (0.39 g, 0.03 equiv, 0.7 mmol), NaOtBu (4.35 g, 2.0 equiv, 45.3 mmol), toluene (113 mL), 2-(4-bromophenyl)naphthalene (7.05 g, 1.1 equiv, 24.9 mmol) and tBu3P (0.46 g, 0.1 equiv, 2.3 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound J19 of a solid (11.66 g, yield 80%).
Through FAB-MS measurement, mass number m/z=643 was observed as an ion peak, and Compound J19 was identified.
Under an Ar atmosphere, to a 500 mL, three-neck flask, IM-42 (15.00 g, 53.8 mmol), Pd(dba)2 (0.93 g, 0.03 equiv, 1.6 mmol), NaOtBu (5.17 g, 1.0 equiv, 53.8 mmol), toluene (269 mL), 4-(dibenzothiophen-4-yl)aniline (16.30 g, 1.1 equiv, 59.2 mmol) and tBu3P (1.09 g, 0.1 equiv, 5.4 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. Organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Intermediate IM-60 (21.45 g, yield 77%).
Through FAB-MS measurement, mass number m/z=517 was observed as an ion peak, and Intermediate IM-60 was identified.
Under an Ar atmosphere, to a 300 mL, three-neck flask, IM-60 (10.00 g, 19.3 mmol), Pd(dba)2 (0.33 g, 0.03 equiv, 0.6 mmol), NaOtBu (3.71 g, 2.0 equiv, 38.6 mmol), toluene (97 mL), 4-(4-bromophenyl)dibenzofuran (6.87 g, 1.1 equiv, 21.2 mmol) and tBu3P (0.39 g, 0.1 equiv, 1.9 mmol) were added in order, and heated, refluxed and stirred. After cooling to room temperature, water was added to the reaction solution, and an organic layer was separately taken. Toluene was added to an aqueous layer, and an organic layer was extracted further. The organic layers were collected, washed with a saline solution, and dried with MgSO4. MgSO4 was filtered, and an organic layer was concentrated. The crude product thus obtained was separated by silica gel column chromatography (utilizing a mixture solvent of hexane and toluene as a developing layer) to obtain Compound K11 of a solid (10.72 g, yield 73%).
Through FAB-MS measurement, mass number m/z=759 was observed as an ion peak, and Compound K11 was identified.
Luminescence devices were manufactured utilizing Example Compounds and Comparative Compounds as materials of a hole transport region.
The luminescence devices of the Examples and Comparative Examples were manufactured by the method below. On a glass substrate, ITO with a thickness of about 150 nm was patterned, washed with ultrapure water and treated with UV ozone to form a first electrode. Then, 2-TNATA was deposited to a thickness of about 60 nm, and an Example Compound or Comparative Compound was deposited to a thickness of about 30 nm to form a hole transport layer. After that, an emission layer was formed utilizing ADN doped with 3% TBP to a thickness of about 25 nm. On the emission layer, a layer with a thickness of about 25 nm was formed utilizing Alq3, and a layer with a thickness of about 1 nm was formed utilizing LiF to form an electron transport region. Then, a second electrode with a thickness of about 100 nm was formed utilizing aluminum (Al). All layers were formed by a vacuum deposition method.
The voltage, emission efficiency and life span of each luminescence device were measured and shown in Table 1 and Table 2 below. The voltage and emission efficiency were measured at a current efficiency of 10 mA/cm2, and the half-life corresponds to results at 1.0 mA/cm2.
Table 1 shows the results on Examples 1 to 19 and Comparative Examples 1 to 10. Table 2 shows the results on Examples 20 to 31 and Comparative Examples 11 to 20. Referring to Table 1 and Table 2, it could be confirmed that Examples 1 to 31 accomplished low voltages, high efficiency and long life span at the same time (e.g., simultaneously) when compared with Comparative Examples 1 to 20.
The amine compound according to embodiments of the present disclosure introduces a substituent into a dibenzofuran or dibenzothiophene skeleton, and shows improved heat resistance and charge tolerance, thereby accomplishing the decrease of a voltage and/or the increase of life span and/or efficiency. In addition, it may be considered that the symmetry of a molecule was degraded (e.g., decreased), and crystallization was restrained (e.g., an amorphous solid form became favored) by the dibenzofuran or dibenzothiophene skeleton having a substituent, and accordingly, layer quality could be improved, hole transport properties could be improved, and emission efficiency could be improved.
In Compound Group 1 shown in Table 1, at least one of R2 or R3 is required to include a dibenzoheterole group as represented by Formula 2-3, but in Compound Groups 2 and 3 shown in Table 2, excellent or suitable device properties were shown even though R2 and R3 are not dibenzoheterole. In case of Compound Group 1 of Table 1, a heteroatom included in Formula 2-1 was influenced by a Rh substituent having a large volume and was covered in three dimensions, and accordingly, the improving effects of hole transport capacity by a heteroatom was degraded. Therefore, by substituting a dibenzoheterole group in R2 or R3, degraded hole transport capacity was improved. In some embodiments, in case of Compound Group 2 or 3 shown in Table 2, a heteroatom included in Formula 2-1 was not covered by a substituent, and sufficient hole transport capacity could be shown.
For example, Examples 1 to 8, 17 to 19, and 27 to 30 were materials in which all multiple dibenzoheterole groups are directly bonded to a nitrogen atom, and particularly, emission efficiency was improved. This is considered that a molecule became compact, intermolecular interaction was strengthened, and hole transport capacity was improved.
Examples 9 to 16, and 29 to 31 were materials in which one selected from among multiple dibenzoheterole groups is bonded to a nitrogen atom via a connecting group, and particularly, device life span was improved. This is estimated that a HOMO orbital was broadly extended to a terminal dibenzoheterole ring via a connecting group, and material stability as a radical or radical cation active species was improved.
Comparative Examples 1 and 2 correspond to amines not having a substituted dibenzoheterole ring, and according to the decrease of the volume of a molecule, intermolecular stacking was improved, the degradation of hole transport capacity was generated, and both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples.
Comparative Example 3 corresponds to an amine in which four phenyl groups are substituted at the same benzene ring moiety of a dibenzoheterole ring, and decomposition of a material was generated under high temperature conditions due to steric repulsion between neighboring phenyl groups, and both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples.
Comparative Example 4 corresponds to a material having a dibenzothiophene group having a substituent at position 6 but is an amine having only one dibenzoheterole group in a molecule, and both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples. It is thought because that the number of dibenzoheterole group is small, the improving effects of hole transport capacity by a heteroatom were reduced, the injection of holes into an emission layer was delayed, and recombination probability in the emission layer was reduced.
Comparative Example 5 corresponds to a material having 4-dibenzothiophene groups as two dibenzoheterole groups, but both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples. When two dibenzothiophene groups are each directly bonded to a nitrogen atom at position 4, the d orbitals of two sulfur atoms in the same molecule may approach and make interaction (e.g., participate in a through-space interaction). Accordingly, intermolecular interaction via heteroatoms between molecules may be reduced, and as a result, hole transport capacity may be reduced.
In some embodiments, as in Example 15, when two dibenzothiophene groups are bonded at each position 4, and when one of them is bonded to a nitrogen atom via a connecting group, and when the bonding positions of two dibenzothiophene groups are different as in Examples 7 and 8, the interaction between two sulfur atoms in a molecule may be relieved, intermolecular interaction between intermolecular heteroatoms may act, and excellent or suitable device characteristics may be shown. In some embodiments, as in Examples 1, 5, 10 and 13, when two dibenzoheterole groups are directly bonded to a nitrogen atom at each position 4, when at least one of the heteroatoms is an oxygen atom, intramolecular interaction between the oxygen atom and the sulfur atom and between the oxygen atom and the oxygen atom is not generated, because the oxygen atom has no d orbital (e.g., the d orbital is not occupied), and excellent or suitable device characteristics may be shown.
Comparative Example 6 is a material having two dibenzoheterole skeletons having a substituent at position 6, but the symmetry of a molecule was improved (e.g., increased), and layer quality was deteriorated due to the increase of crystallinity and decrease of amorphous properties. In addition, because the surroundings of the nitrogen atom are sterically crowded, the material stability under high temperature conditions was deteriorated, and both device efficiency and life spam were degraded (e.g., simultaneously) when compared with the Examples.
In Example 13, though a material has two dibenzoheterole skeletons having a substituent at position 6, when one is bonded to a nitrogen atom via a connecting (e.g., linking) group, the symmetry of a molecule was collapsed, the steric crowd around the nitrogen atom was relieved, the material stability was improved, and excellent or suitable device characteristics were shown.
Comparative Example 7 is a material in which a phenyl group is substituted at a dibenzofuran benzene ring moiety adjacent to where an amine group is bonded. Steric electronic repulsion was generated between the substituents at positions 3 and 4 of the dibenzofuran ring, the surroundings of the nitrogen atom were crowded, material stability under high temperature conditions was degraded, and both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples.
Comparative Example 8 is a material having a carbazole group in a molecule, but carrier balance was collapsed, and both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples.
Comparative Examples 9 and 10 are materials having a silyl group and a fluorene group in a molecule, but both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples. These results are thought to be obtained because a C—Si bond and a sp3 hybrid carbon atom moiety included in the fluorene skeleton were unstable under high temperature conditions, and decomposition was generated during deposition.
Comparative Examples 11 to 13 correspond to amines in which a heterocycle is bonded to (substituted on) a dibenzoheterole ring, but carrier balance was collapsed, and both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples. Comparative Examples 14, 17 and 18 correspond to amines having a fluorene structure in a molecule, but both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples. These results were thought to be obtained because a sp3 hybrid carbon atom moiety included in a fluorene skeleton was unstable, and decomposition was generated during deposition.
Comparative Example 15 corresponds to an amine in which a nitrogen atom is bonded at position 2 of a substituted dibenzoheterole skeleton, and through the improvement of the planarity of a molecule, crystallinity was increased, layer degradation and hole transport capacity degradation were generated, and particularly, device efficiency was degraded when compared with the Examples.
Comparative Example 16 corresponds to an amine having a thiophene ring in a molecule, but because the electron tolerance of the thiophene ring was low, deterioration of a material was generated during driving, and both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples.
Comparative Examples 19 and 10 correspond to amines having two 1-naphthyl groups at the terminal, but both device efficiency and life span were degraded (e.g., simultaneously) when compared with the Examples. It is thought that intermolecular interaction was increased due to the influence of two 1-naphthyl groups in a molecule, and the deposition temperature of a material was increased, and layer forming properties were degraded.
The amine compound according to embodiments of the present disclosure is utilized in a hole transport region, and contributes to the decrease of the driving voltage and the increase of the efficiency and the life span of a luminescence device.
The luminescence device according to embodiments of the present disclosure has excellent or suitable efficiency.
The amine compound according to embodiments of the present disclosure may be utilized as a material of a hole transport region of a luminescence device, and the efficiency of the luminescence device may be improved.
As used herein, the terms “substantially,” “about,” and similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art. “About” or “approximately,” as used herein, is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
Any numerical range recited herein is intended to include all sub-ranges of the same numerical precision subsumed within the recited range. For example, a range of “1.0 to 10.0” is intended to include all subranges between (and including) the recited minimum value of 1.0 and the recited maximum value of 10.0, that is, having a minimum value equal to or greater than 1.0 and a maximum value equal to or less than 10.0, such as, for example, 2.4 to 7.6. Any maximum numerical limitation recited herein is intended to include all lower numerical limitations subsumed therein and any minimum numerical limitation recited in this specification is intended to include all higher numerical limitations subsumed therein. Accordingly, Applicant reserves the right to amend this specification, including the claims, to expressly recite any sub-range subsumed within the ranges expressly recited herein.
Although embodiments of the present disclosure have been described, it is understood that the present disclosure should not be limited to these embodiments, but various suitable changes and modifications can be made by one ordinary skilled in the art within the spirit and scope of the present disclosure as set forth in the following claims and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0012067 | Jan 2021 | KR | national |
