Organic electronic element comprising a compound for organic electronic element and an electronic device thereof
11690292 · 2023-06-27
Assignee
Inventors
- Hyun Ju Song (Cheonan-si, KR)
- Yun Suk Lee (Cheonan-si, KR)
- Hyo Min Jin (Cheonan-si, KR)
- Hyung Dong Lee (Cheonan-si, KR)
Cpc classification
H10K85/631
ELECTRICITY
H10K85/6574
ELECTRICITY
H10K85/626
ELECTRICITY
H10K85/6572
ELECTRICITY
C07B2200/05
CHEMISTRY; METALLURGY
H10K85/633
ELECTRICITY
H10K85/636
ELECTRICITY
H10K85/615
ELECTRICITY
H10K85/6576
ELECTRICITY
Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
Abstract
Provided are an organic electronic element including an anode, a cathode, and an organic material layer between the anode and the cathode, and an electronic device including the organic electronic element, wherein the organic material layer includes each of the compounds represented by Formulas 1 and 2 and the driving voltage of the organic electronic element is lowered, and the luminous efficiency and lifetime of the element are improved.
Claims
1. A compound represented by Formula 1: ##STR00155## wherein: R.sup.1, R.sup.2 and R.sup.3 are each independently selected from the group consisting of hydrogen; deuterium; halogen; and a C.sub.1˜C.sub.60 alkyl group, R.sup.4 is hydrogen; deuterium; a C.sub.6˜C.sub.60 aryl group; or C.sub.6˜C.sub.60 aryl group substituted with deuterium, L.sup.1 is a single bond; or C.sub.6˜C.sub.60 arylene group, Ar.sup.1 is a C.sub.6˜C.sub.60 aryl group, a is an integer of 0 to 5, b is an integer of 0 to 6, c is an integer of 0 to 4, d is an integer of 0 to 7, wherein the alkyl group, aryl group or arylene group may be substituted with one or more substituents selected from the group consisting of deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C.sub.1-C.sub.20 alkylthio group; C.sub.1-C.sub.20 alkoxy group; C.sub.1-C.sub.20 alkyl group; C.sub.2-C.sub.20 alkenyl group; C.sub.2-C.sub.20 alkynyl group; C.sub.6-C.sub.20 aryl group; C.sub.6-C.sub.20 aryl group substituted with deuterium; a fluorenyl group; C.sub.2-C.sub.20 heterocyclic group; C.sub.3-C.sub.20 cycloalkyl group; C.sub.7-C.sub.20 arylalkyl group; and C.sub.8-C.sub.20 arylalkenyl group; and the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term ‘ring’ means a C.sub.3-C.sub.60 aliphatic ring or a C.sub.6-C.sub.60 aromatic ring or a C.sub.2-C.sub.60 heterocyclic group or a fused ring formed by combination thereof.
2. The compound of claim 1, wherein Formula 1 is represented by Formula 1-3 or Formula 1-4: ##STR00156## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.4, a, b, c, L.sup.1 and Ar.sup.1 are the same as defined in claim 1, d′ is an integer from 0 to 6, e is an integer from 0 to 5, and R.sup.5 is hydrogen; or deuterium.
3. The compound of claim 1, wherein Formula 1 is represented by any one of Formulas 1-3-1 to 1-3-3: ##STR00157## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.4, a, b, c, L.sup.1 and Ar.sup.1 are the same as defined in claim 1, d′ is an integer of 0 to 6, e is an integer of 0 to 5, and R.sup.5 is hydrogen; or deuterium.
4. The compound of claim 1, wherein Formula 1 is represented by any one of Formulas 1-4-1 to 1-4-4: ##STR00158## wherein: R.sup.1, R.sup.2, R.sup.3, R.sup.4, a, b, c, L.sup.1 and Ar.sup.1 are the same as defined in claim 1, d′ is an integer of 0 to 6, e is an integer of 0 to 5, and R.sup.5 is hydrogen; or deuterium.
5. The compound of claim 1, wherein, L.sup.1 of Formula 1 is represented by Formula L1 or Formula L2: ##STR00159## wherein: R.sup.6 is hydrogen; or deuterium, f is an integer of 0 to 4, g is an integer of 0 to 6, and * indicates the bonding position.
6. The compound of claim 1, wherein, Ar.sup.1 of Formula 1 is represented by any one of Formulas Ar1 to Ar3: ##STR00160## wherein: R.sup.7 is hydrogen; or deuterium, h is an integer of 0 to 5, i is an integer of 0 to 7, j is an integer of 0 to 9, and * means the bonding position.
7. The compound of claim 1, wherein, Formula 1 is represented by any one of Compounds P-1 to P-104: ##STR00161## ##STR00162## ##STR00163## ##STR00164## ##STR00165## ##STR00166## ##STR00167## ##STR00168## ##STR00169## ##STR00170## ##STR00171## ##STR00172## ##STR00173## ##STR00174## ##STR00175## ##STR00176## ##STR00177## ##STR00178##
8. An organic electronic element comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes an emitting layer, wherein the emitting layer is a phosphorescent emitting layer and comprises a first host compound represented by Formula 1 of claim 1 and a second host compound represented by Formula 2 or Formula 3: ##STR00179## wherein: L.sup.4, L.sup.5, L.sup.6 and L.sup.7 are each independently selected from the group consisting of a single bond; a C.sub.6-C.sub.60 arylene group; fluorenylene group; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; and a C.sub.2-C.sub.60 heterocyclic group, Ar.sup.3, Ar.sup.4 and Ar.sup.5 are each independently selected from the group consisting of a C.sub.6-C.sub.60 aryl group; fluorenyl group; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; and a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring, Ar.sup.6 is selected from the group consisting of a C.sub.6-C.sub.60 aryl group; fluorenyl group; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; and -L′-N(R.sup.b)(R.sup.c), wherein L′ is selected from the group consisting of a single bond; a C.sub.6-C.sub.60 arylene group; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P, and wherein R.sup.b and R.sup.c are each independently selected from the group consisting of a C.sub.6-C.sub.60 aryl group; fluorenyl group; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; C.sub.1-C.sub.50 alkyl group; a C.sub.2-C.sub.20 alkenyl group; a C.sub.2-C.sub.20 alkynyl group; a C.sub.1-C.sub.30 alkoxy group; a C.sub.6-C.sub.30 aryloxy group; Z is O, S, CR′R″ or NRa, B is a C.sub.6-C.sub.20 aryl group, R′ and R″ are each independently selected from the group consisting of a C.sub.6-C.sub.60 aryl group; a fluorenyl group; a C.sub.2-C.sub.60 heterocyclic group including at least one hetero atom of O, N, S, Si or P; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; a C.sub.1-C.sub.50 alkyl group; a C.sub.2-C.sub.20 alkenyl group; a C.sub.2-C.sub.20 alkynyl group; a C.sub.1-C.sub.30 alkoxyl group; and a C.sub.6-C.sub.30 aryloxy group, and R′ and R″ may be bonded to each other to form a ring, R.sup.11 and R.sup.12 are each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; nitro group; a C.sub.6-C.sub.60 aryl group; fluorenyl group; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; a C.sub.1-C.sub.60 alkyl group; a C.sub.2-C.sub.60 alkenyl group; a C.sub.2-C.sub.60 alkynyl group; a C.sub.1-C.sub.60 alkoxy group; and a C.sub.6-C.sub.60 aryloxy group, and a plurality of adjacent R.sup.11 or a plurality of R.sup.12 may be bonded to each other to form a ring, n and o are each independently an integer of 0 to 4, Ra is a C.sub.6-C.sub.60 aryl group; or a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si and P, wherein the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group may be substituted with one or more substituents selected from the group consisting of deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C.sub.1-C.sub.20 alkylthio group; C.sub.1-C.sub.20 alkoxyl group; C.sub.1-C.sub.20 alkyl group; C.sub.2-C.sub.20 alkenyl group; C.sub.2-C.sub.20 alkynyl group; C.sub.6-C.sub.20 aryl group; C.sub.6-C.sub.20 aryl group substituted with deuterium; a fluorenyl group; C.sub.2˜C.sub.20 heterocyclic group; C.sub.3-C.sub.20 cycloalkyl group; C.sub.7-C.sub.20 arylalkyl group; and C.sub.8-C.sub.20 arylalkenyl group, and the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term ‘ring’ means a C.sub.3-C.sub.60 aliphatic ring or a C.sub.6-C.sub.60 aromatic ring or a C.sub.2-C.sub.60 heterocyclic group or a fused ring formed by the combination thereof.
9. The organic electronic element of claim 8, wherein the compound represented by Formula 2 is any one of Compounds N-1 to N-96: ##STR00180## ##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191## ##STR00192## ##STR00193## ##STR00194## ##STR00195## ##STR00196## ##STR00197## ##STR00198## ##STR00199## ##STR00200## ##STR00201## ##STR00202## ##STR00203## ##STR00204## ##STR00205## ##STR00206## ##STR00207## ##STR00208## ##STR00209## ##STR00210## ##STR00211##
10. The organic electronic element of claim 8, wherein the compound represented by Formula 3 is any one of Compounds S-1 to S-108: ##STR00212## ##STR00213## ##STR00214## ##STR00215## ##STR00216## ##STR00217## ##STR00218## ##STR00219## ##STR00220## ##STR00221## ##STR00222## ##STR00223## ##STR00224## ##STR00225## ##STR00226## ##STR00227## ##STR00228## ##STR00229## ##STR00230## ##STR00231## ##STR00232## ##STR00233## ##STR00234## ##STR00235## ##STR00236## ##STR00237## ##STR00238## ##STR00239## ##STR00240## ##STR00241## ##STR00242## ##STR00243## ##STR00244##
11. The organic electronic element of claim 8, wherein the organic electronic element further comprises a light efficiency enhancing layer formed on at least one surface of the first electrode and the second electrode, the surface being opposite to the organic material layer.
12. The organic electronic element of claim 8, wherein the organic material layer comprises 2 or more stacks, each including a hole transport layer, an emitting layer, and an electron transport layer sequentially formed on the first electrode.
13. The organic electronic element of claim 12, wherein the organic material layer further comprises a charge generation layer formed between the 2 or more stacks.
14. An electronic device comprising a display device comprising the organic electronic element of claim 8; and a control unit for driving the display device.
15. The electronic device according to claim 14, wherein the organic electronic element is at least one of an OLED, an organic solar cell, an organic photo conductor (OPC), organic transistor (organic TFT) and an element for monochromic or white illumination.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1)
(2) TABLE-US-00001 100, 200, 300: organic electronic element 110: the first electrode 120: hole injection layer 130: hole transport layer 140: emitting layer 150: electron transport layer 160: electron injection layer 170: second electrode 180: light efficiency enhancing Layer 210: buffer layer 220: emitting-auxiliary layer 320: first hole injection layer 330: first hole transport layer 340: first emitting layer 350: first electron transport layer 360: first charge generation layer 361: second charge generation layer 420: second hole injection layer 430: second hole transport layer 440: second emitting layer 450: second electron transport layer CGL: charge generation layer ST1: first stack ST1: second stack
DETAILED DESCRIPTION OF THE INVENTION
(3) Hereinafter, some embodiments of the present invention will be described in detail. Further, in the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.
(4) In addition, terms, such as first, second, A, B, (a), (b) or the like may be used herein when describing components of the present invention. Each of these terminologies is not used to define an essence, order or sequence of a corresponding component but used merely to distinguish the corresponding component from other component(s). It should be noted that if a component is described as being “connected”, “coupled”, or “connected” to another component, the component may be directly connected or connected to the other component, but another component may be “connected”,” coupled” or “connected” between each component.
(5) As used in the specification and the accompanying claims, unless otherwise stated, the following is the meaning of the term as follows.
(6) Unless otherwise stated, the term “halo” or “halogen”, as used herein, includes fluorine, bromine, chlorine, or iodine.
(7) Unless otherwise stated, the term “alkyl” or “alkyl group”, as used herein, has a single bond of 1 to 60 carbon atoms, and means saturated aliphatic functional radicals including a linear alkyl group, a branched chain alkyl group, a cycloalkyl group (alicyclic), an cycloalkyl group substituted with a alkyl or an alkyl group substituted with a cycloalkyl.
(8) Unless otherwise stated, the term “alkenyl” or “alkynyl”, as used herein, has double or triple bonds of 2 to 60 carbon atoms, but is not limited thereto, and includes a linear or a branched chain group.
(9) Unless otherwise stated, the term “cycloalkyl”, as used herein, means alkyl forming a ring having 3 to 60 carbon atoms, but is not limited thereto.
(10) Unless otherwise stated, the term “alkoxyl group”, “alkoxy group” or “alkyloxy group”, as used herein, means an oxygen radical attached to an alkyl group, but is not limited thereto, and has 1 to 60 carbon atoms.
(11) Unless otherwise stated, the term “aryloxyl group” or “aryloxy group”, as used herein, means an oxygen radical attached to an aryl group, but is not limited thereto, and has 6 to 60 carbon atoms.
(12) Unless otherwise stated, the term “aryl group” or “arylene group”, as used herein, has 6 to 60 carbon atoms, but is not limited thereto. Herein, the aryl group or arylene group means a monocyclic and polycyclic aromatic group, and may also be formed in conjunction with an adjacent group. Examples of “aryl group” may include a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.
(13) The prefix “aryl” or “ar” means a radical substituted with an aryl group. For example, an arylalkyl may be an alkyl substituted with an aryl, and an arylalenyl may be an alkenyl substituted with aryl, and a radical substituted with an aryl has a number of carbon atoms as defined herein.
(14) Also, when prefixes are named subsequently, it means that substituents are listed in the order described first. For example, an arylalkoxy means an alkoxy substituted with an aryl, an alkoxylcarbonyl means a carbonyl substituted with an alkoxyl, and an arylcarbonylalkenyl also means an alkenyl substituted with an arylcarbonyl, wherein the arylcarbonyl may be a carbonyl substituted with an aryl.
(15) Unless otherwise stated, the term “heterocyclic group”, as used herein, contains one or more heteroatoms, but is not limited thereto, has 2 to 60 carbon atoms, includes any one of monocyclic and polycyclic rings, and may include heteroaliphadic ring and/or heteroaromatic ring. Also, the heterocyclic group may also be formed in conjunction with an adjacent group.
(16) Unless otherwise stated, the term “heteroatom”, as used herein, represents at least one of N, O, S, P, or Si.
(17) Also, the term “heterocyclic group” may include a ring including SO.sub.2 instead of carbon consisting of cycle. For example, “heterocyclic group” includes the following compound.
(18) ##STR00002##
(19) Unless otherwise stated, the term “fluorenyl group” or “fluorenylene group”, as used herein, means a monovalent or divalent functional group, in which R, R′ and R″ are all hydrogen in the following structures, and the term “substituted fluorenyl group” or “substituted fluorenylene group” means that at least one of the substituents R, R′, R″ is a substituent other than hydrogen, and include those in which R and R′ are bonded to each other to form a spiro compound together with the carbon to which they are bonded.
(20) ##STR00003##
(21) The term “spiro compound”, as used herein, has a ‘spiro union’, and a spiro union means a connection in which two rings share only one atom. At this time, atoms shared in the two rings are called ‘spiro atoms’, and these compounds are called ‘monospiro-’, ‘di-spiro’ and ‘tri-spiro’, respectively, depending on the number of atoms in a compound.
(22) Unless otherwise stated, the term “aliphatic”, as used herein, means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the term “aliphatic ring”, as used herein, means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.
(23) Unless otherwise stated, the term “ring”, as used herein, means an aliphatic ring having 3 to 60 carbon atoms, or an aromatic ring having 6 to 60 carbon atoms, or a hetero ring having 2 to 60 carbon atoms, or a fused ring formed by the combination of them, and includes a saturated or unsaturated ring.
(24) Other hetero compounds or hetero radicals other than the above-mentioned hetero compounds include, but are not limited thereto, one or more heteroatoms.
(25) Unless otherwise stated, the term “substituted or unsubstituted”, as used herein, means that substitution is substituted by at least one substituent selected from the group consisting of, but is not limited thereto, deuterium, halogen, an amino group, a nitrile group, a nitro group, a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkoxyl group, a C.sub.1-C.sub.20 alkylamine group, a C.sub.1-C.sub.20 alkylthiopen group, a C.sub.6-C.sub.20 arylthiopen group, a C.sub.2-C.sub.20 alkenyl group, a C.sub.2-C.sub.20 alkynyl group, a C.sub.3-C.sub.20 cycloalkyl group, a C.sub.6-C.sub.20 aryl group, a C.sub.6-C.sub.20 aryl group substituted by deuterium, a C.sub.8-C.sub.20 arylalkenyl group, a silane group, a boron group, a germanium group, and a C.sub.2-C.sub.20 heterocyclic group.
(26) Unless otherwise expressly stated, the Formula used in the present invention, as used herein, is applied in the same manner as the substituent definition according to the definition of the exponent of the following Formula.
(27) ##STR00004##
(28) here, when a is an integer of zero, the substituent R.sup.1 is absent, when a is an integer of 1, the sole substituent R.sup.1 is linked to any one of the carbon constituting the benzene ring, when a is an integer of 2 or 3, each substituent R.sup.1s may be the same and different, when a is an integer of 4 to 6, and is linked to the benzene ring in a similar manner, whereas the indication of hydrogen bound to the carbon forming the benzene ring is omitted.
(29) ##STR00005##
(30) Hereinafter, a laminated structure of an organic electronic device including the compound of the present invention will be described with reference to
(31) In adding reference numerals to elements of each figure, it should be noted that the same elements have the same numerals as possible even if they are indicated on different figures.
(32) In addition, in describing the present invention, when it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a detailed description thereof will be omitted.
(33)
(34) Referring to
(35) The first electrode (110) may be an anode, the second electrode (170) may be a cathode, and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.
(36) The organic material layer may include a hole injection layer (120), a hole transport layer (130), an emitting layer (140), an electron transport layer (150), and an electron injection layer (160). Specifically, a hole injection layer (120), a hole transport layer (130), an emitting layer (140), an electron transport layer (150), and an electron injection layer (160) may be sequentially formed on the first electrode (110).
(37) The present invention may further include a light efficiency enhancing layer formed on one of not in contact with the organic material layer among one side of the first electrode (110) or of the second electrode (170), and when the light efficiency enhancing layer (180) is formed, the light efficiency of the organic electronic element may be improved.
(38) For example, the light efficiency enhancing layer (180) may be formed on the second electrode (170), and in the case of a top emission organic light emitting device, the light efficiency enhancing layer (180) is formed, thereby reducing optical energy loss due to surface plasmon polaritons (SPPs) in the second electrode (170), and in the case of a bottom emission organic light emitting device, the light efficiency enhancing layer (180) may function as a buffer for the second electrode (170).
(39) A buffer layer (210) or an emitting auxiliary layer (220) may be further formed between the hole transport layer (130) and the emitting layer (140), which will be described with reference to
(40) Referring to
(41) Although not shown in
(42) Also, according to another embodiment of the present invention, the organic material layer may have a plurality of stacks including a hole transport layer, an emitting layer, and an electron transport layer. This will be described with reference to
(43) Referring to
(44) Specifically, the organic electronic element according to an embodiment of the present invention includes a first electrode (110), a first stack (ST1), a charge generation layer (CGL), a second stack (ST2), and a second electrode. (170) and a light efficiency enhancing layer (180) may be included.
(45) The first stack (ST1) is an organic material layer formed on the first electrode (110) and may include a first hole injection layer (320), a first hole transport layer (330), a first emitting layer (340), and a first electron transport layer (350), and the second stack (ST2) may include a second hole injection layer (420), a second hole transport layer (430), a second emitting layer (440), and a second electron transport layer (450). As described above, the first stack and the second stack may be organic material layers having the same laminated structure, but may be organic material layers having different laminated structures.
(46) A charge generation layer (CGL) may be formed between the first stack (ST1) and the second stack (ST2). The charge generation layer (CGL) may include a first charge generation layer (360) and a second charge generation layer (361). The charge generation layer (CGL) is formed between the first emitting layer (340) and the second emitting layer (440) to increase the current efficiency generated in each emitting layer and smoothly distribute charge.
(47) When a plurality of emitting layers are formed by the multilayer stack structure method as shown in
(48) The compounds represented by Formulas 1 and 2 of the present invention may be used as a material fora hole injection layer (120, 320, 420), a hole transport layer (130, 330, 430), a buffer layer (210), an emitting auxiliary layer (220), and an electron transport layer (150, 350, 450), the electron injection layer (160), the emitting layer (140, 340, 440), or the light efficiency enhancing layer (180), but preferably, the compounds represented by Formulas 1 and 2 of the present invention may be used as a host of the emitting layers (140, 340, 440).
(49) Otherwise, even if the same or similar core is used, the band gap, the electrical characteristics, the interface characteristics, and the like may vary depending on which substituent is bonded at which position, therefore the choice of core and the combination of sub-substituents associated therewith is also very important, and in particular, when the optimal combination of energy levels and T1 values and unique properties of materials (mobility, interfacial characteristics, etc.) of each organic material layer is achieved, a long lifespan and high efficiency can be achieved at the same time.
(50) The organic electronic element according to an embodiment of the present invention may be manufactured using various deposition methods. It can be manufactured using a vapor deposition method such as PVD or CVD. For example, an anode (110) is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and after forming an organic material layer including the hole injection layer (120), the hole transport layer (130), the emitting layer (140), the electron transport layer (150) and the electron injection layer (160) thereon, the organic electroluminescent device according to an embodiment of the present invention can be manufactured by depositing a material that can be used as a cathode (170) thereon. Also, an emitting auxiliary layer (220) may be further formed between the hole transport layer (130) and the emitting layer (140), and an electron transport auxiliary layer (not shown) may be further formed between the emitting layer (140) and the electron transport layer (150), and as described above, may be formed in a stack structure.
(51) Also, the organic material layer may be manufactured with a smaller number of layers by using various polymer materials and not by a deposition method, but by a solution process, a solvent process, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process, doctor blading process, screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.
(52) In addition, the organic electric device according to an embodiment of the present invention may be selected from the group consisting of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, a monochromatic lighting device, and a quantum dot display device.
(53) Another embodiment of the present invention may include an electronic device comprising a display device including the organic electronic element; and a control unit for driving the display device. At this time, the electronic device may be a current or future wired/wireless communication terminal, and covers all kinds of electronic devices including a mobile communication terminal such as a cellular phone, a personal digital assistant (PDA), an electronic dictionary, a point-to-multipoint (PMP), a remote controller, a navigation unit, a game player, various kinds of TVs, and various kinds of computers.
(54) Hereinafter, an organic electronic element according to an aspect of the present invention will be described.
(55) The present invention provides a compound represented by Formula 1.
(56) ##STR00006##
(57) Wherein:
(58) R.sup.1, R.sup.2 and R.sup.3 are each the same or different, and each independently hydrogen; deuterium; halogen; or a C.sub.1˜C.sub.60 alkyl group;
(59) R.sup.4 is hydrogen; deuterium; a C.sub.6˜C.sub.60 aryl group; or C.sub.6˜C.sub.60 aryl group substituted with deuterium;
(60) L.sup.1 is a single bond; or C.sub.6˜C.sub.60 arylene group,
(61) wherein in case R.sup.4 is a substituted or unsubstituted group, it is preferably an C.sub.6-C.sub.30 aryl group, more preferably an C.sub.6-C.sub.24 aryl group, for example, it may be phenylene, biphenyl, naphthalene, terphenyl, and the like.
(62) Ar.sup.1 is C.sub.6˜C.sub.60 aryl group, preferably an C.sub.6-C.sub.30 aryl group, more preferably an C.sub.6-C.sub.24 aryl group, for example, it may be phenylene, biphenyl, naphthalene, terphenyl, and the like.
(63) a is an integer from 0 to 5, b is an integer from 0 to 6, c is an integer from 0 to 4, d is an integer from 0 to 7, wherein, the alkyl group, aryl group or arylene group may be substituted with one or more substituents selected from the group consisting of deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C.sub.1-C.sub.20 alkylthio group; C.sub.1-C.sub.20 alkoxy group; C.sub.1-C.sub.20 alkyl group; C.sub.2-C.sub.20 alkenyl group; C.sub.2-C.sub.20 alkynyl group; C.sub.6-C.sub.20 aryl group; C.sub.6-C.sub.20 aryl group substituted with deuterium; a fluorenyl group; C.sub.2˜C.sub.20 heterocyclic group; C.sub.3-C.sub.20 cycloalkyl group; C.sub.7-C.sub.20 arylalkyl group; and C.sub.8-C.sub.20 arylalkenyl group; also the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term ‘ring’ means a C.sub.3-C.sub.60 aliphatic ring or a C.sub.6-C.sub.60 aromatic ring or a C.sub.2-C.sub.60 heterocyclic group or a fused ring formed by the combination thereof.
(64) Also, Formula 1 is represented by Formula 1-1 or Formula 1-2.
(65) ##STR00007##
(66) Wherein R.sup.1, R.sup.2, R.sup.3, a, b, c, L.sup.1 and Ar.sup.1 are the same as defined in Formula 1.
(67) Also, Formula 1 is represented by Formula 1-3 or Formula 1-4.
(68) ##STR00008##
(69) Wherein:
(70) R.sup.1, R.sup.2, R.sup.3, R.sup.4, a, b, c, L.sup.1 and Ar.sup.1 are the same as defined in Formula 1.
(71) d is an integer from 0 to 6, e is an integer from 0 to 5,
(72) R.sup.5 is hydrogen; or deuterium.
(73) Also, Formula 1 is represented by any one of Formulas 1-3-1 to 1-3-3.
(74) ##STR00009##
(75) Wherein:
(76) R.sup.1, R.sup.2, R.sup.3, R.sup.4, a, b, c, L.sup.1 and Ar.sup.1 are the same as defined in Formula 1,
(77) d′ is an integer from 0 to 6, e is an integer from 0 to 5,
(78) R.sup.5 is hydrogen; or deuterium.
(79) Also, Formula 1 is represented by any one of Formulas 1-4-1 to 1-4-4.
(80) ##STR00010##
(81) Wherein:
(82) R.sup.1, R.sup.2, R.sup.3, R.sup.4, a, b, c, L.sup.1 and Ar.sup.1 are the same as defined in Formula 1,
(83) d′ is an integer from 0 to 6, e is an integer from 0 to 5,
(84) R.sup.5 is hydrogen; or deuterium.
(85) Also, L.sup.1 of Formula 1 is represented by Formula L1 or Formula L2
(86) ##STR00011##
(87) Wherein:
(88) R.sup.6 is hydrogen; or deuterium;
(89) f is an integer from 0 to 4, g is an integer from 0 to 6,
(90) * means the bonding position.
(91) Also, Ar.sup.1 of Formula 1 is represented by any one of Formulas Ar1 to Ar3
(92) ##STR00012##
(93) Wherein:
(94) R.sup.7 is hydrogen; or deuterium;
(95) h is an integer from 0 to 5, i is an integer from 0 to 7, j is an integer from 0 to 9,
(96) * means the bonding position.
(97) Also, the compound represented by Formula 1 is represented by any one of the following compounds P-1 to P-104.
(98) ##STR00013## ##STR00014## ##STR00015## ##STR00016## ##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021## ##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026## ##STR00027## ##STR00028##
(99) Also, the present invention relates to an organic electronic element comprising a first electrode, a second electrode, and an organic material layer formed between the first electrode and the second electrode, wherein the organic material layer includes an emitting layer, wherein the emitting layer is a phosphorescent emitting layer, and comprises a first host compound represented by Formula 1 of claim 1 and a second host compound represented by Formula 2 or Formula 3.
(100) ##STR00029##
(101) Wherein:
(102) L.sup.4, L.sup.5, L.sup.6 and L.sup.7 are each independently selected from the group consisting of a single bond; a C.sub.6-C.sub.60 arylene group; fluorenylene group; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; a C.sub.2-C.sub.60 heterocyclic group;
(103) wherein in case L.sup.4, L.sup.5, L.sup.6 and L.sup.7 are an arylene group, it is preferably an C.sub.6-C.sub.30 arylene group, more preferably an C.sub.6-C.sub.24 arylene group, for example, it may be phenylene, biphenyl, naphthalene, terphenyl, and the like.
(104) when L.sup.4, L.sup.5, L.sup.6 and L.sup.7 are a heterocyclic group, it is preferably a C.sub.2-C.sub.30 heterocyclic group, and more preferably a C.sub.2-C.sub.24 heterocyclic group, for example, it may be Pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazole, dibenzofuran, Benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine.
(105) when L.sup.4, L.sup.5, L.sup.6 and L.sup.7 are a fused ring group, it is preferably a fused ring group of an C.sub.3-C.sub.30 aliphatic ring and an C.sub.6-C.sub.30 aromatic ring, and more preferably a fused ring group of an C.sub.3-C.sub.24 aliphatic ring and an C.sub.6-C.sub.24 aromatic ring,
(106) Ar.sup.3, Ar.sup.4 and Ar.sup.5 are each independently selected from the group consisting of a C.sub.6-C.sub.60 aryl group; fluorenyl group; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; and a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring;
Ar.sup.6 is each independently selected from the group consisting of a C.sub.6-C.sub.60 aryl group; fluorenyl group; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; and -L′-N(R.sup.b)(R.sup.c);
(107) When Ar.sup.3, Ar.sup.4, Ar.sup.5 and Ar.sup.6 are an aryl group, it is preferably an C.sub.6-C.sub.30 aryl group, more preferably an C.sub.6-C.sub.24 aryl group, for example, it may be phenylene, biphenyl, naphthalene, terphenyl, and the like.
(108) When Ar.sup.3, Ar.sup.4, Ar.sup.5 and Ar.sup.6 are a heterocyclic group, it is preferably a C.sub.2-C.sub.30 heterocyclic group, and more preferably a C.sub.2-C.sub.24 heterocyclic group, for example, it may be Pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazole, dibenzofuran, Benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine.
(109) when Ar.sup.3, Ar.sup.4, Ar.sup.5 and Ar.sup.6 are a fused ring group, it is preferably a fused ring group of an C.sub.3-C.sub.30 aliphatic ring and an C.sub.6-C.sub.30 aromatic ring, and more preferably a fused ring group of an C.sub.3-C.sub.24 aliphatic ring and an C.sub.6-C.sub.24 aromatic ring,
(110) Wherein L′ is selected from the group consisting of a single bond; a C.sub.6-C.sub.60 arylene group; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P;
(111) Wherein R.sup.b and R.sup.c are each independently selected from the group consisting of a C.sub.6-C.sub.60 aryl group; fluorenyl group; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; C.sub.1-C.sub.50 alkyl group; a C.sub.2-C.sub.20 alkenyl group; a C.sub.2-C.sub.20 alkynyl group; a C.sub.1-C.sub.30 alkoxy group; a C.sub.6-C.sub.30 aryloxy group;
(112) Z is O, S, CR′R″ or NRa,
(113) B is a C.sub.6˜C.sub.20 aryl group,
(114) R′ and R″ are each independently selected from a group consisting of a C.sub.6-C.sub.60 aryl group; a fluorenyl group; a C.sub.2-C.sub.60 heterocyclic group including at least one hetero atom of O, N, S, Si or P; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; a C.sub.1-C.sub.50 alkyl group; a C.sub.2-C.sub.20 alkenyl group; a C.sub.2-C.sub.20 alkynyl group; a C.sub.1-C.sub.30 alkoxyl group; and a C.sub.6-C.sub.30 aryloxy group; or may be bonded to each other to form a ring,
(115) R.sup.11 and R.sup.12 are each independently the same as or different from each other, and each independently selected from the group consisting of hydrogen; deuterium; halogen; cyano group; nitro group; a C.sub.6-C.sub.60 aryl group; fluorenyl group; a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si or P; a fused ring group of a C.sub.3-C.sub.60 aliphatic ring and a C.sub.6-C.sub.60 aromatic ring; a C.sub.1-C.sub.6 alkyl group; a C.sub.2-C.sub.60 alkenyl group; a C.sub.2-C.sub.60 alkynyl group; a C.sub.1-C.sub.60 alkoxy group; and a C.sub.6-C.sub.60 aryloxy group; or a plurality of adjacent R.sup.11 or a plurality of R.sup.12 may be bonded to each other to form a ring,
(116) When R′, R″, R.sup.11 and R.sup.12 are an aryl group, it is preferably an C.sub.6-C.sub.30 aryl group, more preferably an C.sub.6-C.sub.24 aryl group, for example, it may be phenylene, biphenyl, naphthalene, terphenyl, and the like.
(117) When R′, R″, R.sup.11 and R.sup.12 are a heterocyclic group, it is preferably a C.sub.2-C.sub.30 heterocyclic group, and more preferably a C.sub.2-C.sub.24 heterocyclic group, for example, it may be Pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazole, dibenzofuran, Benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine.
(118) when R′, R″, R.sup.11 and R.sup.12 are a fused ring group, it is preferably a fused ring group of an C.sub.3-C.sub.30 aliphatic ring and an C.sub.6-C.sub.30 aromatic ring, and more preferably a fused ring group of an C.sub.3-C.sub.24 aliphatic ring and an C.sub.6-C.sub.24 aromatic ring,
(119) when R′, R″, R.sup.11 and R.sup.12 are an alkyl group, it is preferably a C.sub.1-C.sub.30 alkyl group, and more preferably a C.sub.1-C.sub.24 alkyl group.
(120) when R′, R″, R.sup.11 and R.sup.12 are an alkoxyl group, it is preferably a C.sub.1-C.sub.24 alkoxyl group.
(121) when R′, R″, R.sup.11 and R.sup.12 are an aryloxy group, it is preferably a C.sub.1-C.sub.24 aryloxy group.
(122) n and o are each independently an integer from 0 to 4,
(123) Ra is a C.sub.6-C.sub.60 aryl group; or a C.sub.2-C.sub.60 heterocyclic group including at least one heteroatom of O, N, S, Si and P;
(124) When Ra is an aryl group, it is preferably an C.sub.6-C.sub.30 aryl group, more preferably an C.sub.6-C.sub.24 aryl group, for example, it may be phenylene, biphenyl, naphthalene, terphenyl, and the like.
(125) When Ra is a heterocyclic group, it is preferably a C.sub.2-C.sub.30 heterocyclic group, and more preferably a C.sub.2-C.sub.24 heterocyclic group, for example, it may be Pyrazine, thiophene, pyridine, pyrimidoindole, 5-phenyl-5H-pyrimido[5,4-b]indole, quinazoline, benzoquinazoline, carbazole, dibenzoquinazole, dibenzofuran, Benzothienopyrimidine, benzofuropyrimidine, phenothiazine, phenylphenothiazine.
(126) wherein the aryl group, arylene group, heterocyclic group, fluorenyl group, fluorenylene group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group may be substituted with one or more substituents selected from the group consisting of deuterium; halogen; silane group; siloxane group; boron group; germanium group; cyano group; nitro group; C.sub.1-C.sub.20 alkylthio group; C.sub.1-C.sub.20 alkoxyl group; C.sub.1-C.sub.20 alkyl group; C.sub.2-C.sub.20 alkenyl group; C.sub.2-C.sub.20 alkynyl group; C.sub.6-C.sub.20 aryl group; C.sub.6-C.sub.20 aryl group substituted with deuterium; a fluorenyl group; C.sub.2˜C.sub.20 heterocyclic group; C.sub.3-C.sub.20 cycloalkyl group; C.sub.7-C.sub.20 arylalkyl group; and C.sub.8-C.sub.20 arylalkenyl group; and also the substituents may be bonded to each other to form a saturated or unsaturated ring, wherein the term ‘ring’ means a C.sub.3-C.sub.60 aliphatic ring or a C.sub.6-C.sub.60 aromatic ring or a C.sub.2-C.sub.60 heterocyclic group or a fused ring formed by the combination thereof.
(127) Formula 2 is represented by any one of Formulas 2-1 to 2-3.
(128) ##STR00030##
(129) Wherein:
(130) Ar.sup.4, Ar.sup.5, L.sup.4, L.sup.5 and L.sup.6 are the same as defined in Formula 2,
(131) X.sup.1, X.sup.2 and X.sup.3 are the same as defined for Z,
(132) R.sup.13, R.sup.14, R.sup.15, R.sup.16, R.sup.17 and R.sup.16 are the same as the definition of R.sup.11, or a plurality of adjacent R.sup.13s or a plurality of R.sup.14s or a plurality of R.sup.15s or a plurality of R.sup.16s or a plurality of R.sup.17s or a plurality of R.sup.1s may be bonded to each other to form a ring, p, r and t are an integer of 0 to 4, q, s and u are each independently an integer from 0 to 3.
(133) Formula 3 is represented by any one of Formulas 3-1 to 3-6.
(134) ##STR00031## ##STR00032##
(135) Wherein:
(136) Z, R.sup.11, R.sup.12, Ar.sup.6, L.sup.7, n, o are the same as defined in Formula 3,
(137) R.sup.19 is the same as the definition of R.sup.11,
(138) v is an integer from 0 to 2.
(139) Formula 3 is represented by any one of Formulas 3-7 to 3-9.
(140) ##STR00033##
(141) Wherein:
(142) Z, B, R.sup.12, o, Ar.sup.6 and L.sup.7 are the same as defined in Formula 3,
(143) R.sup.20 is the same as the definition of R.sup.11,
(144) w is an integer from 0 to 6
(145) Formula 3 is represented by any one of Formulas 3-10 to 3-12.
(146) ##STR00034##
(147) Wherein:
(148) Z, B, Ar.sup.6, L.sup.7, R.sup.11 and n are the same as defined in Formula 3,
(149) R.sup.21 is the same as definition of R.sup.11,
(150) x is an integer from 0 to 6.
(151) Formula 3 is represented by Formulas 3-13 to 3-18.
(152) ##STR00035## ##STR00036##
(153) Wherein:
(154) Z, L.sup.7, Ar.sup.6, R.sup.11, R.sup.12, n and o are the same as defined in Formula 3,
(155) R.sup.19, R.sup.20 and R.sup.21 are the same as the definition of R.sup.11,
(156) v is an integer from 0 to 2, w and x are each independently an integer from 0 to 6.
(157) Formula 3 is represented by Formula 3-19.
(158) ##STR00037##
(159) wherein:
(160) L.sup.7, Ar.sup.6, Ra, R.sup.12 and o are the same as defined in Formula 3,
(161) R.sup.19 and R.sup.20 are the same as the definition of R.sup.11,
(162) v is an integer from 0 to 2, w is an integer from 0 to 6.
(163) Also, the compound represented by Formula 2 is any one of the following compounds N-1 to N-96.
(164) ##STR00038## ##STR00039## ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044## ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049## ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055## ##STR00056## ##STR00057## ##STR00058## ##STR00059## ##STR00060## ##STR00061## ##STR00062## ##STR00063## ##STR00064## ##STR00065## ##STR00066## ##STR00067## ##STR00068## ##STR00069##
(165) Also, the compound represented by Formula 3 is any one of the following compounds S-1 to S-108.
(166) ##STR00070## ##STR00071## ##STR00072## ##STR00073## ##STR00074## ##STR00075## ##STR00076## ##STR00077## ##STR00078## ##STR00079## ##STR00080## ##STR00081## ##STR00082## ##STR00083## ##STR00084## ##STR00085## ##STR00086## ##STR00087## ##STR00088## ##STR00089## ##STR00090## ##STR00091## ##STR00092## ##STR00093## ##STR00094## ##STR00095## ##STR00096## ##STR00097## ##STR00098## ##STR00099## ##STR00100## ##STR00101## ##STR00102##
(167) The present invention may further include a light efficiency enhancing layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.
(168) Also, the organic material layer may include 2 or more stacks including a hole transport layer, an emitting layer, and an electron transport layer sequentially formed on the anode, and the organic material layer may further include a charge generation layer formed between the 2 or more stacks.
(169) In another aspect, the present invention provides an electronic device comprising a display device including the organic electronic element; and a control unit for driving the display device; here, the organic electronic element is at least one of an OLED, an organic solar cell, an organic photo conductor, an organic transistor and an element for monochromic or white illumination.
(170) Hereinafter, Synthesis Examples of the compound represented by Formula according to the present invention and preparation examples of the organic electronic element according to the present invention will be described in detail by way of example, but are not limited to the following examples of the invention.
SYNTHESIS EXAMPLE
(171) The compound was synthesized as follows.
(172) The compound (final products) represented by Formula 1 according to the present invention is represented by <Reaction Scheme 1>, but is not limited thereto.
(173) ##STR00103##
I. Synthesis of Core
(174) Core of <Reaction Scheme 1> may be synthesized by the reaction route of <Reaction Scheme 2>, but is not limited thereto.
(175) ##STR00104##
1. Synthesis Example of Core 5
(176) ##STR00105##
(1) Synthesis of Core a-5-1
(177) 1-bromobenzene-2,3,4,5,6-d5 (50 g, 1 eqiv.), (4-chloronaphthalen-1-yl)boronic acid (63.7 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (10.7 g, 0.03 eqiv.), K.sub.2CO.sub.3 (128 g, 2 eqiv.), THE (1030 mL, 0.3 M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 45.1 g of Core a-5-1 (yield: 60%).
(2) Synthesis of Core a-5
(178) core a-5-1 (45 g, 1 eqiv.), (3-chlorophenyl)boronic acid (43.4 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (9.6 g, 0.03 eqiv.), K.sub.2CO.sub.3 (115 g, 2 eqiv.), THE (925 mL, 0.3 M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 48 g of Core a-5 (yield: 55%).
(3) Synthesis of Core 5
(179) Core a-5 (45 g, 1 eqiv.), bis(pinacolato)diboron (43 g, 1.2 eqiv.), Pd.sub.2 (dba).sub.3 (3.9 g, 0.03 eqiv.), X-phos (2.3 g, 0.06 equiv.), KOAc (41 g, 2 eqiv.) were dissolved in Toluene (470 mL, 0.3 M) in a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 41 g of Core 5 (yield: 71%).
2. Synthesis Example of Core 6
(180) ##STR00106##
(1) Synthesis of Core a-6-1
(181) 1-bromobenzene (38 g, 1 eqiv.), (4-chloronaphthalen-1-yl)boronic acid (50 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (8.4 g, 0.03 eqiv.), K.sub.2CO.sub.3 (100 g, 2 eqiv.), THE (807 mL, 0.3 M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 31 g of Core a-6-1 (yield: 53%).
(2) Synthesis of Core a-6
(182) Core a-6-1 (30 g, 1 eqiv.), (3-chlorophenyl)boronic acid (20 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (4.4 g, 0.03 eqiv.), K.sub.2CO.sub.3 (52 g, 2 eqiv.), THE (419 mL, 0.3 M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 26 g of Core a-6 (yield: 66%).
(3) Synthesis of Core 6
(183) Core a-6 (25 g, 1 eqiv.), bis(pinacolato)diboron (24 g, 1.2 eqiv.), Pd.sub.2 (dba).sub.3 (2.2 g, 0.03 eqiv.), X-phos (2.3 g, 0.06 equiv.), KOAc (24 g, 2 eqiv.) were dissolved in Toluene (265 mL, 0.3 M) in a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 25 g of Core 6 (yield: 80%).
3. Synthesis Example of Core 17
(184) ##STR00107##
(1) Synthesis of Core a-17-1
(185) 1-bromobenzene-2,3,4,5,6-d5 (50 g, 1 eqiv.), (4-chloronaphthalen-1-yl)boronic acid (63.7 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (10.7 g, 0.03 eqiv.), K.sub.2CO.sub.3 (128 g, 2 eqiv.), THE (1030 mL, 0.3 M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 56 g of Core a-17-1 (yield: 78%).
(2) Synthesis of Core a-17
(186) Core a-17-1 (55 g, 1 eqiv.), (3-chlorophenyl)boronic acid (35 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (7.8 g, 0.03 eqiv.), K.sub.2CO.sub.3 (94 g, 2 eqiv.), THE (750 mL, 0.3 M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 46 g of Core a-17 (yield: 64%).
(3) Synthesis of Core 17
(187) Core a-17 (45 g, 1 eqiv.), bis(pinacolato)diboron (43 g, 1.2 eqiv.), Pd.sub.2 (dba).sub.3 (3.9 g, 0.03 eqiv.), X-phos (4.0 g, 0.06 equiv.), KOAc (41 g, 2 eqiv.) were dissolved in Toluene (470 mL, 0.3 M) in a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 42 g of Core 17 (yield: 73%).
4. Synthesis Example of Core 20
(188) ##STR00108##
(1) Synthesis of Core a-20-1
(189) 2-bromonaphthalene (50 g, 1 eqiv.), (5-chloronaphthalen-1-yl)boronic acid (50 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (8.4 g, 0.03 eqiv.), K.sub.2CO.sub.3 (100 g, 2 eqiv.), THE (800 mL, 0.3 M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 58 g of Core a-20-1 (yield: 83%).
(2) Synthesis of Core a-20
(190) Core a-20-1 (39 g, 1 eqiv.), (3-chlorophenyl)boronic acid (21 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (4.7 g, 0.03 eqiv.), K.sub.2CO.sub.3 (56 g, 2 eqiv.), THE (450 mL, 0.3 M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 32 g of Core a-20 (yield: 66%).
(3) Synthesis of Core 20
(191) Core a-20 (32 g, 1 eqiv.), bis(pinacolato) diboron (27 g, 1.2 eqiv.), Pd.sub.2 (dba).sub.3 (2.4 g, 0.03 eqiv.), X-phos (2.5 g, 0.06 equiv.), KOAc (26 g, 2 eqiv.) were dissolved in Toluene (290 mL, 0.3 M) in a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 25 g of Core 20 (yield: 63%).
5. Synthesis Example of Core 33
(192) ##STR00109##
(1) Synthesis of Core a-33
(193) 1-bromonaphthalene-2,3,4,5,6,7,8-d7 (50 g, 1 eqiv.), (3-chlorophenyl) boronic acid (36.5 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (8.1 g, 0.03 eqiv.), K.sub.2CO.sub.3 (97 g, 2 eqiv.), THE (778 mL, 0.3M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 38.5 g of Core a-33 (yield: 67%).
(2) Synthesis of Core 33
(194) Core a-33 (30 g, 1 eqiv.), bis(pinacolato) diboron (37.2 g, 1.2 eqiv.), Pd.sub.2 (dba).sub.3 (3.4 g, 0.03 eqiv.), X-phos (4.0 g, 0.06 equiv.), KOAc (36 g, 2 eqiv.) were dissolved in Toluene (407 mL, 0.3 M) in a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 32.9 g of Core 33 (yield: 80%).
6. Synthesis Example of Core 34
(195) ##STR00110##
(1) Synthesis of Core a-34-1
(196) 1-bromonaphthalene-2,3,4,5,6,7,8-d7 (50 g, 1 eqiv.), (4-chloronaphthalen-1-yl)boronic acid (48 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (8.1 g, 0.03 eqiv.), K.sub.2CO.sub.3 (97 g, 2 eqiv.), THE (780 mL, 0.3M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 49 g of Core a-34-1 (yield: 71%).
(2) Synthesis of Core a-34
(197) Core a-34-1 (49 g, 1 eqiv.), (3-chlorophenyl)boronic acid (26 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (5.7 g, 0.03 eqiv.), K.sub.2CO.sub.3 (69 g, 2 eqiv.), THE (550 mL, 0.3M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 47 g of Core a-34 (yield: 77%).
(3) Synthesis of Core 34
(198) Core a-34 (45 g, 1 eqiv.), bis(pinacolato)diboron (37 g, 1.2 eqiv), Pd.sub.2 (dba).sub.3 (3.3 g, 0.03 eqiv.), X-Phos (3.5 g, 0.06 equiv.), KOAc (35 g, 2 eqiv.) were dissolved in Toluene (400 mL, 0.3 M) in a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 38 g of Core 34 (yield: 68%).
7. Synthesis Example of Core 35
(199) ##STR00111##
(1) Synthesis of Core a-35-1
(200) 1-bromonaphthalene-2,3,4,5,6,7,8-d7 (50 g, 1 eqiv.), (4-chloronaphthalen-1-yl)boronic acid (48.2 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (8.1 g, 0.03 eqiv.), K.sub.2CO.sub.3 (97 g, 2 eqiv.), THE (780 mL, 0.3M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 54 g of Core a-35-1 (yield: 79%).
(2) Synthesis of Core a-35
(201) Core a-35-1 (54 g, 1 eqiv.), (3-chlorophenyl)boronic acid (28.5 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (6.3 g, 0.03 eqiv.), K.sub.2CO.sub.3 (76 g, 2 eqiv.), THE (600 mL, 0.3M), water were added to a round bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 46 g of Core a-35 (yield: 68%).
(3) Synthesis of Core 35
(202) Core a-35 (45 g, 1 eqiv.), bis(pinacolato) diboron (37 g, 1.2 eqiv.), Pd.sub.2 (dba).sub.3 (3.3 g, 0.03 eqiv.), X-Phos (3.5 g, 0.06 equiv.), KOAc (36 g, 2 eqiv.) were dissolved in Toluene (400 mL, 0.3 M) in a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 43 g of Core 35 (yield: 77%).
(203) Meanwhile, the compound belonging to Core may be the following compounds, but is not limited thereto, and Table 1 shows the FD-MS (Field Desorption-Mass Spectrometry) values of the compounds belonging to Core.
(204) ##STR00112## ##STR00113## ##STR00114## ##STR00115## ##STR00116## ##STR00117## ##STR00118## ##STR00119## ##STR00120##
(205) TABLE-US-00002 TABLE 1 Cpd. FD-MS Core1 m/z = 330.18(C.sub.22H.sub.23BO.sub.2 = 330.23) Core2 m/z = 338.23(C.sub.22H.sub.15D.sub.8BO.sub.2 = 338.28) Core3 m/z = 339.24(C.sub.22H.sub.14D.sub.9BO.sub.2 = 339.29) Core4 m/z = 340.24(C.sub.22H.sub.13D.sub.10BO.sub.2 = 340.30) Core5 m/z = 411.24(C.sub.28H.sub.22D.sub.5BO.sub.2 = 411.36) Core6 m/z = 406.21(C.sub.28H.sub.27BO.sub.2 = 406.33) Core7 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core8 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core9 m/z = 411.24(C.sub.28H.sub.22D.sub.5BO.sub.2 = 411.36) Core10 m/z = 406.21(C.sub.28H.sub.27BO.sub.2 = 406.33) Core11 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core12 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core13 m/z = 411.24(C.sub.28H.sub.22D.sub.5BO.sub.2 = 411.36) Core14 m/z = 406.21(C.sub.28H.sub.27BO.sub.2 = 406.33) Core15 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core16 m/z = 456.23(C.sub.32H.sub.29 BO.sub.2 = 456.39) Core17 m/z = 411.24(C.sub.28H.sub.22D.sub.5BO.sub.2 = 411.36) Core18 m/z = 406.21(C.sub.28H.sub.27BO.sub.2 = 406.33) Core19 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core20 m/z = 456.23(C.sub.32H.sub.29 BO.sub.2 = 456.39) Core21 m/z = 411.24(C.sub.28H.sub.22D.sub.5BO.sub.2 = 411.36) Core22 m/z = 406.21(C.sub.28H.sub.27BO.sub.2 = 406.33) Core23 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core24 m/z = 456.23(C.sub.32H.sub.29 BO.sub.2 = 456.39) Core25 m/z = 411.24(C.sub.28H.sub.22D.sub.5BO.sub.2 = 411.36) Core26 m/z = 406.21(C.sub.28H.sub.27BO.sub.2 = 406.33) Core27 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core28 m/z = 456.23(C.sub.32H.sub.29 BO.sub.2 = 456.39) Core29 m/z = 411.24(C.sub.28H.sub.22D.sub.5BO.sub.2 = 411.36) Core30 m/z = 406.21(C.sub.28H.sub.27BO.sub.2 = 406.33) Core31 m/z = 456.23(C.sub.32H.sub.29BO.sub.2 = 456.39) Core32 m/z = 456.23(C.sub.32H.sub.29 BO.sub.2 = 456.39) Core33 m/z = 337.22(C.sub.22H.sub.16D.sub.7BO.sub.2 = 337.28) Core34 m/z = 463.27(C.sub.32H.sub.22D.sub.7BO.sub.2 = 463.43) Core35 m/z = 463.27(C.sub.32H.sub.22D.sub.7BO.sub.2 = 463.43)
II. Synthesis of Sub
(206) Sub of <Reaction Scheme 1> may be synthesized by the reaction route of <Reaction Scheme 3>, but is not limited thereto.
(207) ##STR00121##
1. Synthesis Example of Sub 1
(208) ##STR00122##
(209) 2,4-dichloro-6-phenyl-1,3,5-triazine (30 g, 2 equiv.), Sub 1-1 (22 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (2.3 g, 0.03 equiv.), K.sub.2CO.sub.3 (28 g, 2 equiv.), Toluene (220 mL, 0.3M) and water were added to a round-bottom flask and stirred at 50° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 12 g of Sub 1 (yield: 48%).
2. Synthesis Example of Sub 2
(210) ##STR00123##
(211) 2,4-dichloro-6-phenyl-1,3,5-triazine (30 g, 2 equiv.), Sub1-1 (18 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (1.9 g, 0.03 equiv.), K.sub.2CO.sub.3 (23 g, 2 equiv.), Toluene (180 mL, 0.3M) and water were added to a round-bottom flask and stirred at 50° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 11 g of Sub 2 (yield: 45%).
3. Synthesis Example of Sub 26
(212) ##STR00124##
2,4-dichloro-6-phenyl-1,3,5-triazine (30 g, 2 equiv.), Sub 26-1 (22 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (2.3 g, 0.03 equiv.), K.sub.2CO.sub.3 (28 g, 2 equiv.), Toluene (220 mL, 0.3M) and water were added to a round-bottom flask and stirred at 50° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 11 g of Sub 26 (yield: 43%).
4. Synthesis Example of Sub 41
(213) ##STR00125##
(1) Synthesis of Sub b-41-1
(214) 1-bromo-3-iodobenzene (25 g, 2 eqiv.), naphthalen-1-ylboronic acid (30 g, 1 eqiv.), Pd(PPh.sub.3).sub.4 (3 g, 0.03 eqiv.), K.sub.2CO.sub.3 (36 g, 2 eqiv.), THE (300 mL, 0.3M) and water were added to a round-bottom flask and stirred at 80° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 18 g of Sub b-41-1 (yield: 75%).
(2) Synthesis of Sub b-41
(215) Add Mg (5.3 g, 2 eqiv.) and THE (360 mL, 0.3M) to round-bottom flask 1 filled with nitrogen and stir at 50° C., then slowly add sub b-41-1 (20 g, 1 eqiv.) dropwise. After 6 hours, stop stirring and take the solution using a syringe. 2,4,6-trichloro-1,3,5-triazine (40 g, 2 eqiv.) was dissolved in THE in round bottom flask 2, and Grignard reagent was slowly added dropwise, followed by stirring for 12 hours. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 15 g of Sub b-41 (yield: 40%).
(3) Synthesis of Sub 41
(216) 2,4-dichloro-6-phenyl-1,3,5-triazine (30 g, 2 equiv.), Sub 26-1 (14 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (1.5 g, 0.03 equiv.), K.sub.2CO.sub.3 (18 g, 2 equiv.), Toluene (140 mL, 0.3M) and water were added to a round-bottom flask and stirred at 50° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 9 g of Sub 41 (yield: 40%).
(217) Otherwise, the compound belonging to Sub may be the following compounds, but is not limited thereto, and Table 2 shows the FD-MS values of the compounds belonging to Sub.
(218) ##STR00126## ##STR00127## ##STR00128## ##STR00129## ##STR00130## ##STR00131## ##STR00132## ##STR00133## ##STR00134## ##STR00135## ##STR00136## ##STR00137## ##STR00138##
(219) TABLE-US-00003 TABLE 2 Cpd. FD-MS sub1 m/z = 393.10(C.sub.25H.sub.16CIN.sub.3 = 393.87) sub2 m/z = 443.12(C.sub.29H.sub.18CIN.sub.3 = 443.93) sub3 m/z = 443.12(C.sub.29H.sub.18CIN.sub.3 = 443.93) sub4 m/z = 469.13(C.sub.31H.sub.20CIN.sub.3 = 469.97) sub5 m/z = 469.13(C.sub.31H.sub.20CIN.sub.3 = 469.97) sub6 m/z = 469.13(C.sub.31H.sub.20CIN.sub.3 = 469.97) sub7 m/z = 493.13(C.sub.33H.sub.20CIN.sub.3 = 493.99) sub8 m/z = 493.13(C.sub.33H.sub.20CIN.sub.3 = 493.99) sub9 m/z = 493.13(C.sub.33H.sub.20CIN.sub.3 = 493.99) sub10 m/z = 493.13(C.sub.33H.sub.20CIN.sub.3 = 493.99) sub11 m/z = 493.13(C.sub.33H.sub.20CIN.sub.3 = 493.99) sub12 m/z = 543.15(C.sub.37H.sub.22CIN.sub.3 = 544.05) sub13 m/z = 493.13(C.sub.33H.sub.20CIN.sub.3 = 493.99) sub14 m/z = 493.13(C.sub.33H.sub.20CIN.sub.3 = 493.99) sub15 m/z = 543.15(C.sub.37H.sub.22CIN.sub.3 = 544.05) sub16 m/z = 519.15(C.sub.35H.sub.22CIN.sub.3 = 520.03) sub17 m/z = 519.15(C.sub.35H.sub.22CIN.sub.3 = 520.03) sub18 m/z = 519.15(C.sub.35H.sub.22CIN.sub.3 = 520.03) sub19 m/z = 543.15(C.sub.37H.sub.22CIN.sub.3 = 544.05) sub20 m/z = 519.15(C.sub.35H.sub.22CIN.sub.3 = 520.03) sub21 m/z = 519.15(C35H22CIN3 = 520.03) sub22 m/z = 519.15(C.sub.35H.sub.22CIN.sub.3 = 520.03) sub23 m/z = 519.15(C.sub.35H.sub.22CIN.sub.3 = 520.03) sub24 m/z = 519.15(C.sub.35H.sub.22CIN.sub.3 = 520.03) sub25 m/z = 519.15(C.sub.35H.sub.22CIN.sub.3 = 520.03) sub26 m/z = 398.13(C.sub.25H.sub.11D.sub.5CIN.sub.3 = 398.90) sub27 m/z = 448.15(C.sub.29H.sub.13D.sub.5CIN.sub.3 = 448.96) sub28 m/z = 448.15(C.sub.29H.sub.13D.sub.5CIN.sub.3 = 448.96) sub29 m/z = 474.17(C.sub.31H.sub.15D.sub.5CIN.sub.3 = 475.00) sub30 m/z = 474.17(C.sub.31H.sub.15D.sub.5CIN.sub.3 = 475.00) sub31 m/z = 474.17(C.sub.31H.sub.15D.sub.5CIN.sub.3 = 475.00) sub32 m/z = 498.17(C.sub.33H.sub.15D.sub.5CIN.sub.3 = 499.02) sub33 m/z = 498.17(C.sub.33H.sub.15D.sub.5CIN.sub.3 = 499.02) sub34 m/z = 498.17(C.sub.33H.sub.15D.sub.5CIN.sub.3 = 499.02) sub35 m/z = 498.17(C.sub.33H.sub.15D.sub.5CIN.sub.3 = 499.02) sub36 m/z = 498.17(C.sub.33H.sub.15D.sub.5CIN.sub.3 = 499.02) sub37 m/z = 548.18(C.sub.37H.sub.17D.sub.5CIN.sub.3 = 549.08) sub38 m/z = 548.18(C.sub.37H.sub.17D.sub.5CIN.sub.3 = 549.08) sub39 m/z = 498.17(C.sub.33H.sub.15D.sub.5CIN.sub.3 = 499.02) sub40 m/z = 548.18(C.sub.37H.sub.17D.sub.5CIN.sub.3 = 549.08) sub41 m/z = 524.18(C.sub.35H.sub.17D.sub.5CIN.sub.3 = 525.06) sub42 m/z = 524.18(C.sub.35H.sub.17D.sub.5CIN.sub.3 = 525.06) sub43 m/z = 524.18(C.sub.35H.sub.17D.sub.5CIN.sub.3 = 525.06) sub44 m/z = 524.18(C.sub.35H.sub.17D.sub.5CIN.sub.3 = 525.06) sub45 m/z = 524.18(C.sub.35H.sub.17D.sub.5CIN.sub.3 = 525.06)
III. Synthesis of Final Product
1. Synthesis Example of P-1
(220) ##STR00139##
(221) Core 1 (8.4 g, 1 equiv.), sub 1 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.9 g, 0.03 equiv.), K.sub.2CO.sub.3 (10.5 g, 2 equiv.), Toluene (44 mL), Ethanol (5 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 11 g of P-1 (yield: 77%).
2. Synthesis Example of P-22
(222) ##STR00140##
(223) Core 6 (10.3 g, 1 equiv.), sub 1 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.9 g, 0.03 equiv.), K.sub.2CO.sub.3 (10.5 g, 2 equiv.), Toluene (85 mL), Ethanol (9 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 134 g of P-22 (yield: 83%).
3. Synthesis Example of P-43
(224) ##STR00141##
(225) Core 33 (6.9 g, 1 equiv.), sub 2 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.7 g, 0.03 equiv.), K.sub.2CO.sub.3 (8.5 g, 2 equiv.), Toluene (68 mL), Ethanol (7 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 8.5 g of P-43 (yield: 67%).
4. Synthesis Example of P-63
(226) ##STR00142##
(227) Core 5 (9.5 g, 1 equiv.), sub 1 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.8 g, 0.03 equiv.), K.sub.2CO.sub.3 (9.6 g, 2 equiv.), Toluene (77 mL), Ethanol (8 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 10.4 g of P-63 (yield: 70%).
5. Synthesis Example of P-66
(228) ##STR00143##
(229) Core 17 (9.5 g, 1 equiv.), sub 1 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.8 g, 0.03 equiv.), K.sub.2CO.sub.3 (9.6 g, 2 equiv.), Toluene (77 mL), Ethanol (8 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 9.8 g of P-66 (yield: 66%).
6. Synthesis Example of P-72
(230) ##STR00144##
(231) Core 34 (11.8 g, 1 equiv.), sub 1 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.9 g, 0.03 equiv.), K.sub.2CO.sub.3 (10.5 g, 2 equiv.), Toluene (85 mL), Ethanol (8 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 12.9 g of P-72 (yield: 73%).
7. Synthesis Example of P-83
(232) ##STR00145##
(233) Core 5 (10.3 g, 1 equiv.), sub 26 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.9 g, 0.03 equiv.), K.sub.2CO.sub.3 (10.4 g, 2 equiv.), Toluene (84 mL), Ethanol (8 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 8.9 g of P-83 (yield: 55%).
8. Synthesis Example of P-92
(234) ##STR00146##
(235) Core 33 (6.4 g, 1 equiv.), sub 41 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.7 g, 0.03 equiv.), K.sub.2CO.sub.3 (7.9 g, 2 equiv.), Toluene (64 mL), Ethanol (6 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 9.8 g of P-92 (yield: 74%).
9. Synthesis Example of P-98
(236) ##STR00147##
(237) Core 6 (8.5 g, 1 equiv.), sub 26 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.9 g, 0.03 equiv.), K.sub.2CO.sub.3 (10.4 g, 2 equiv.), Toluene (84 mL), Ethanol (8 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 9.8 g of P-98 (yield: 61%).
10. Synthesis Example of P-102
(238) ##STR00148##
(239) Core 20 (11.4 g, 1 equiv.), sub 26 (10 g, 1 equiv.), Pd(PPh.sub.3).sub.4 (0.9 g, 0.03 equiv.), K.sub.2CO.sub.3 (10.4 g, 2 equiv.), Toluene (84 mL), Ethanol (8 mL) and water were added to a round-bottom flask and stirred at 120° C. When the reaction was completed, the resulting compound was extracted with CH.sub.2Cl.sub.2 and water, the organic layer was dried over MgSO.sub.4, concentrated, and the resulting compound was recrystallized by silicagel column to obtain 9.2 g of P-102 (yield: 53%).
(240) Besides, the FD-MS values of the compounds P-1 to P-104 of the present invention prepared according to the above synthesis examples are shown in Table 3.
(241) TABLE-US-00004 TABLE 3 Cpd. FD-MS P-1 m/z = 561.22(C.sub.41H.sub.27N.sub.3 = 561.69) P-2 m/z = 611.24(C.sub.45H.sub.29N.sub.3 = 611.75) P-3 m/z = 611.24(C.sub.45H.sub.29N.sub.3 = 611.75) P-4 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-5 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-6 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-7 m/z = 661.25(C.sub.49H.sub.31N.sub.3 = 661 .81) P-8 m/z = 661.25(C.sub.49H.sub.31N.sub.3 = 661 .81) P-9 m/z = 711.27(C.sub.53H.sub.33N.sub.3 = 711.87) P-10 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-11 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-12 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-13 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-14 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-15 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-16 m/z = 737.28(C.sub.55H.sub.35N.sub.3 = 737.91) P-17 m/z = 737.28(C.sub.55H.sub.35N.sub.3 = 737.91) P-18 m/z = 737.28(C.sub.55H.sub.35N.sub.3 = 737.91) P-19 m/z = 763.30(C.sub.57H.sub.37N.sub.3 = 763.94) P-20 m/z = 763.30(C.sub.57H.sub.37N.sub.3 = 763.94) P-21 m/z = 763.30(C.sub.57H.sub.37N.sub.3 = 763.94) P-22 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-23 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-24 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-25 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-26 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-27 m/z = 637.25(C.sub.47H.sub.31N.sub.3 = 637.79) P-28 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-29 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-30 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-31 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-32 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-33 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-34 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-35 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-36 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-37 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-38 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-39 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-40 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-41 m/z = 687.27(C.sub.51H.sub.33N.sub.3 = 687.85) P-42 m/z = 568.26(C.sub.41H.sub.20D.sub.7N.sub.3 = 568.73) P-43 m/z = 618.28(C.sub.45H.sub.22D.sub.7N.sub.3 = 618.79) P-44 m/z = 618.28(C.sub.45H.sub.22D.sub.7N.sub.3 = 6 18.79) P-45 m/z = 644.30(C.sub.47H.sub.24D.sub.7N.sub.3 = 644.83) P-46 m/z = 644.30(C.sub.47H.sub.24D.sub.7N.sub.3 = 644.83) P-47 m/z = 644.30(C.sub.47H.sub.24D.sub.7N.sub.3 = 644.83) P-48 m/z = 668.30(C.sub.49H.sub.24D.sub.7N.sub.3 = 668.85) P-49 m/z = 668.30(C.sub.49H.sub.24D.sub.7N.sub.3 = 668.85) P-50 m/z = 718.31(C.sub.53H.sub.26D.sub.7N.sub.3 = 718.91) P-51 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-52 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-53 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-54 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-55 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-56 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-57 m/z = 770.34(C.sub.57H.sub.30D.sub.7N= = 770.99) P-58 m/z = 744.33(C.sub.55H.sub.28D.sub.7N.sub.3 = 744.95) P-59 m/z = 744.33(C.sub.55H.sub.28D.sub.7N.sub.3 = 744.95) P-60 m/z = 770.34(C.sub.57H.sub.30D.sub.7N.sub.3 = 770.99) P-61 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-62 m/z = 770.34(C.sub.57H.sub.30D.sub.7N.sub.3 = 770.99) P-63 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-64 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-65 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-66 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-67 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-68 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-69 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-70 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-71 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-72 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-73 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-74 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-75 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-76 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-77 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-78 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-79 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-80 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-81 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-82 m/z = 694.31(C.sub.51H.sub.26D.sub.7N.sub.3 = 694.89) P-83 m/z = 647.31(C.sub.47H.sub.21D.sub.10N.sub.3 = 647.85) P-84 m/z = 647.31(C.sub.47H.sub.21D.sub.10N.sub.3 = 647.85) P-85 m/z = 647.31(C.sub.47H.sub.21D.sub.10N.sub.3 = 647.85) P-86 m/z = 699.34(C.sub.51H.sub.21D.sub.12N.sub.3 = 699.92) P-87 m/z = 573.30(C.sub.41H.sub.15D.sub.12N.sub.3 = 573.76) P-88 m/z = 623.31(C.sub.45H.sub.17D.sub.12N.sub.3 = 623.82) P-89 m/z = 623.31(C.sub.45H.sub.17D.sub.12N.sub.3 = 623.82) P-90 m/z = 649.33(C.sub.47H.sub.19D.sub.12N.sub.3 = 649.86) P-91 m/z = 699.34(C.sub.51H.sub.21D.sub.12N.sub.3 = 699.92) P-92 m/z = 699.34(C.sub.51H.sub.21D.sub.12N.sub.3 = 699.92) P-93 m/z = 699.34(C.sub.51H.sub.21D.sub.12N.sub.3 = 699.92) P-94 m/z = 699.34(C.sub.51H.sub.21D.sub.12N.sub.3 = 699.92) P-95 m/z = 699.34(C.sub.51H.sub.21D.sub.12N.sub.3 = 699.92) P-96 m/z = 699.34(C.sub.51H.sub.21D.sub.12N.sub.3 = 699.92) P-97 m/z = 699.34(C.sub.51H.sub.21D.sub.12N.sub.3 = 699.92) P-98 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-99 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-100 m/z = 642.28(C.sub.47H.sub.26D.sub.5N.sub.3 = 642.82) P-101 m/z = 692.30(C.sub.51H.sub.28D.sub.5N.sub.3 = 692.88) P-102 m/z = 692.30(C.sub.51H.sub.28D.sub.5N.sub.3 = 692.88) P-103 m/z = 692.30(C.sub.51H.sub.28D.sub.5N.sub.3 = 692.88) P-104 m/z = 692.30(C.sub.51H.sub.28D.sub.5N.sub.3 = 692.88)
Synthesis Example 2
1. Synthesis Example of N-12
(242) ##STR00149##
(243) N-12a (30 g, 0.08 mol), N-12b (34.8 g, 0.08 mol), Pd.sub.2(dba).sub.3 (2.3 g, 0.003 mol), NaOt-Bu (24.5 g, 0.25 mol), P(t-Bu).sub.3 (2.1 g, 0.005 mol), Toluene (170 mL) were added and reacted at 135° C. for 6 hours. When the reaction was completed, 53 g (85.8%) of the product N-12 was obtained by using the separation method for P-1.
2. Synthesis Example of N-19
(244) ##STR00150##
(245) N-19a (50 g, 0.13 mol), N-19b (35 g, 0.13 mol), Pd.sub.2(dba).sub.3 (3.6 g, 0.004 mol), NaOt-Bu (37.6 g, 0.40 mol), P(t-Bu).sub.3 (3.2 g, 0.008 mol), Toluene (260 mL) were added and reacted at 135° C. for 6 hours. When the reaction was completed, 67 g (83.4%) of the product N-19 was obtained by using the separation method for P-1.
3. Synthesis Example of S-32
(246) ##STR00151##
(247) S-32a (10 g, 0.04 mol), S-32b (15.6 g, 0.04 mol), Pd.sub.2(dba).sub.3 (1.1 g, 0.001 mol), NaOt-Bu (11.7 g, 0.12 mol), P(t-Bu).sub.3 (1.0 g, 0.002 mol), Toluene (80 mL) were added and reacted at 135° C. for 6 hours. When the reaction was completed, 18 g (80.8%) of the product S-32 was obtained by using the separation method for P-1.
4. Synthesis Example of S-74
(248) ##STR00152##
(249) S-74a (15 g, 0.06 mol), S-74b (20.9 g, 0.06 mol), Pd.sub.2(dba).sub.3 (1.6 g, 0.002 mol), NaOt-Bu (16.9 g, 0.18 mol), P(t-Bu).sub.3 (1.4 g, 0.004 mol), Toluene (120 mL) were added and reacted at 135° C. for 6 hours. When the reaction was completed, 27 g (86.4%) of the product S-74 was obtained by using the separation method for P-1.
5. Synthesis Example of S-104
(250) ##STR00153##
(251) S-104a (30 g, 0.13 mol), S-104b (48.2.9 g, 0.13 mol), Pd.sub.2(dba).sub.3 (3.5 g, 0.004 mol), NaOt-Bu (36.4 g, 0.38 mol), P(t-Bu).sub.3 (3.1 g, 0.008 mol), Toluene (250 mL) were added and reacted at 135° C. for 6 hours. When the reaction was completed, 60 g (81.5%) of the product S-104 was obtained by using the separation method for P-1.
(252) Meanwhile, FD-MS values of compounds N-1 to N-96 and S-1 to S-108 of the present invention prepared according to the above synthesis examples are shown in Tables 4 and 5.
(253) TABLE-US-00005 TABLE 4 Cpd. FD-MS N-1 m/z = 487.19(C.sub.36H.sub.25NO = 487.6) N-2 m/z = 553.19(C.sub.40H.sub.27NS = 553.72) N-3 m/z = 563.26(C.sub.43H.sub.33N = 563.74) N-4 m/z = 602.27(C.sub.45H.sub.34N.sub.2 = 602.78) N-5 m/z = 517.15(C.sub.36H.sub.23NOS = 517.65) N-6 m/z = 603.2(C.sub.44H.sub.29NS = 603.78) N-7 m/z = 735.29(C.sub.57H.sub.37N = 735.93) N-8 m/z = 562.24(C.sub.42H.sub.30N.sub.2 = 562.72) N-9 m/z = 565.17(C.sub.40H.sub.23NO.sub.3 = 565.63) N-10 m/z = 581.14(C.sub.40H.sub.23NO.sub.2S = 581.69) N-11 m/z = 823.24(C.sub.59H.sub.37NS.sub.2 = 824.07) N-12 m/z = 727.3(C.sub.54H.sub.37N.sub.3 = 727.91) N-13 m/z = 627.22(C.sub.46H.sub.29NO.sub.2 = 627.74) N-14 m/z = 633.16(C.sub.44H.sub.27NS.sub.2 = 633.83) N-15 m/z = 675.29(C.sub.52H.sub.37N = 675.88) N-16 m/z = 678.3(C.sub.51H.sub.38N.sub.2 = 678.88) N-17 m/z = 669.21(C.sub.48H.sub.31NOS = 669.84) N-18 m/z = 785.22(C.sub.56H.sub.35NS.sub.2 = 786.02) N-19 m/z = 617.18(C.sub.44H.sub.27NOS = 617.77) N-20 m/z = 601.2(C.sub.44H.sub.27NO.sub.2 = 601.71) N-21 m/z = 779.32(C.sub.59H.sub.41NO = 779.98) N-22 m/z = 583.23(C.sub.42H.sub.33NS = 583.79) N-23 m/z = 679.32(C.sub.52H.sub.41N = 679.91) N-24 m/z = 726.27(C.sub.54H.sub.34N.sub.2O = 726.88) N-25 m/z = 593.18(C.sub.42H.sub.27NOS = 593.74) N-26 m/z = 774.22(C.sub.54H.sub.34N.sub.2S.sub.2 = 775) N-27 m/z = 557.24(C.sub.40H.sub.31NO.sub.2 = 557.69) N-28 m/z = 652.25(C.sub.48H.sub.32N.sub.2O = 652.8) N-29 m/z = 619.29(C.sub.46H.sub.37NO = 619.81) N-30 m/z = 603.2(C.sub.44H.sub.29NS = 603.78) N-31 m/z = 813.3(C.sub.62H.sub.39NO = 814) N-32 m/z = 784.29(C.sub.57H.sub.40N.sub.2S = 785.02) N-33 m/z = 577.2(C.sub.42H.sub.27NO.sub.2 = 577.68) N-34 m/z = 607.14(C.sub.42H.sub.25NS.sub.2 = 607.79) N-35 m/z = 801.34(C.sub.62H.sub.43N = 802.03) N-36 m/z = 575.24(C.sub.42H.sub.29N3 = 575.72) N-37 m/z = 577.2(C.sub.42H.sub.27NO.sub.2 = 577.68) N-38 m/z = 607.14(C.sub.42H.sub.25NS.sub.2 = 607.79) N-39 m/z = 801.34(C.sub.62H.sub.43N = 802.03) N-40 m/z = 575.24(C.sub.42H.sub.29N.sub.3 = 575.72) N-41 m/z = 601.2(C.sub.44H.sub.27NO.sub.2 = 601.71) N-42 m/z = 471.11(C.sub.31H.sub.21NS.sub.2 = 471.64) N-43 m/z = 675.29(C.sub.52H.sub.37N = 675.88) N-44 m/z = 727.3(C.sub.54H.sub.37N.sub.3 = 727.91) N-45 m/z = 603.2(C.sub.44H.sub.29NS = 603.78) N-46 m/z = 561.16(C.sub.38H.sub.27NS.sub.2 = 561.76) N-47 m/z = 799.32(C.sub.62H.sub.41N = 800.02) N-48 m/z = 702.27(C.sub.52H.sub.34N.sub.2O = 702.86) N-49 m/z = 729.27(C.sub.54H.sub.35NO.sub.2 = 729.88) N-50 m/z = 785.22(C.sub.56H.sub.35NS.sub.2 = 786.02) N-51 m/z = 812.32(C.sub.62H.sub.40N.sub.2 = 813.02) N-52 m/z = 681.22(C.sub.48H.sub.31N.sub.3S = 681.86) N-53 m/z = 615.18(C.sub.44H.sub.25NO.sub.3 = 61 5.69) N-54 m/z = 763.15(C.sub.52H.sub.29NS.sub.3 = 763.99) N-55 m/z = 593.31(C.sub.45H.sub.39N = 593.81) N-56 m/z = 840.33(C.sub.62H.sub.40N.sub.4 = 841.03) N-57 m/z = 657.18(C.sub.46H.sub.27NO.sub.2S = 657.79) N-58 m/z = 824.23(C.sub.58H.sub.36N.sub.2S.sub.2 = 825.06) N-59 m/z = 1195.42(C.sub.91H.sub.57NS = 1196.52) N-60 m/z = 656.19(C.sub.46H.sub.28N.sub.2OS = 656.8) N-61 m/z = 607.16(C.sub.42H.sub.25NO.sub.2S = 607.73) N-62 m/z = 773.2(C.sub.54H.sub.31NO.sub.3S = 773.91) N-63 m/z = 1013.4(C.sub.79H.sub.51N = 1014.28) N-64 m/z = 758.24(C.sub.54H.sub.34N.sub.2OS = 758.94) N-65 m/z = 623.14(C.sub.42H.sub.25NOS.sub.2 = 623.79) N-66 m/z = 763.16(C.sub.52H.sub.29NO.sub.2S.sub.2 = 763.93) N-67 m/z = 799.2(C.sub.56H.sub.33NOS.sub.2 = 800.01) N-68 m/z = 743.23(C.sub.54H.sub.33NOS = 743.92) N-69 m/z = 872.25(C.sub.62H.sub.36N.sub.2O.sub.2S = 873.04) N-70 m/z = 772.22(C.sub.54H.sub.32N.sub.2O.sub.2S = 772.92) N-71 m/z = 830.28(C.sub.61H.sub.38N.sub.2S = 831.05) N-72 m/z = 808.25(C.sub.58H.sub.33FN.sub.2O.sub.2 = 808.91) N-73 m/z = 929.21(C.sub.64H.sub.35NO.sub.3S.sub.2 = 930.11) N-74 m/z = 963.27(C.sub.68H.sub.41N.sub.3S.sub.2 = 964.22) N-75 m/z = 809.24(C.sub.58H.sub.35NO.sub.2S = 809.98) N-76 m/z = 893.29(C.sub.66H.sub.39NO.sub.3 = 894.04) N-77 m/z = 794.28(C.sub.58H.sub.38N.sub.2S = 795.02) N-78 m/z = 900.26(C.sub.64H.sub.40N.sub.2S.sub.2 = 901.16) N-79 m/z = 758.28(C.sub.55H.sub.38N.sub.2S = 758.98) N-80 m/z = 1082.37(C.sub.81H.sub.50N.sub.2S = 1083.37) N-81 m/z = 573.25(C.sub.44H.sub.31N = 573.74) N-82 m/z = 649.28(C.sub.50H.sub.35N = 649.84) N-83 m/z = 699.29(C.sub.54H.sub.37N = 699.9) N-84 m/z = 699.29(C.sub.54H.sub.37N = 699.9) N-85 m/z = 673.28(C.sub.52H.sub.35N = 673.86) N-86 m/z = 649.28(C.sub.50H.sub.35N = 649.84) N-87 m/z = 625.28(C.sub.48H.sub.35N = 625.82) N-88 m/z = 673.28(C.sub.52H.sub.35N = 673.86) N-89 m/z = 773.31(C.sub.60H.sub.39N = 773.98) N-90 m/z = 749.31(C.sub.58H.sub.39N = 749.96) N-91 m/z = 699.29(C.sub.54H.sub.37N = 699.9) N-92 m/z = 599.26(C.sub.46H.sub.33N = 599.78) N-93 m/z = 639.26(C.sub.48H.sub.33NO = 639.8) N-94 m/z = 765.25(C.sub.57H.sub.35NS = 765.97) N-95 m/z = 677.31(C.sub.52H.sub.39N = 677.89) N-96 m/z = 727.3(C.sub.54H.sub.37N.sub.3 = 727.91)
(254) TABLE-US-00006 TABLE 5 Cpd. FD-MS S-1 m/z = 408.16(C.sub.30H.sub.20N.sub.2 = 408.5) S-2 m/z = 534.21(C.sub.40H.sub.26N.sub.2 = 534.66) S-3 m/z = 560.23(C.sub.42H.sub.28N.sub.2 = 560.7) S-4 m/z = 584.23(C.sub.44H.sub.28N.sub.2 = 584.72) S-5 m/z = 560.23(C.sub.42H.sub.28N.sub.2 = 560.7) S-6 m/z = 634.24(C.sub.48H.sub.30N.sub.2 = 634.78) S-7 m/z = 610.24(C.sub.46H.sub.30N.sub.2 = 610.76) S-8 m/z = 498.17(C.sub.36H.sub.22N.sub.2O = 498.59) S-9 m/z = 574.2(C.sub.42H.sub.26N.sub.2O = 574.68) S-10 m/z = 660.26(C.sub.50H.sub.32N.sub.2 = 660.82) S-11 m/z = 686.27(C.sub.52H.sub.34N.sub.2 = 686.86) S-12 m/z = 620.14(C.sub.42H.sub.24N.sub.2S.sub.2 = 620.79) S-13 m/z = 640.2(C.sub.46H.sub.28N.sub.2S = 640.8) S-14 m/z = 560.23(C.sub.42H.sub.28N.sub.2 = 560.7) S-15 m/z = 558.21(C.sub.42H.sub.26N.sub.2 = 558.68) S-16 m/z = 548.19(C.sub.40H.sub.24N.sub.2O = 548.65) S-17 m/z = 573.22(C.sub.42H.sub.27N.sub.3 = 573.7) S-18 m/z = 564.17(C.sub.40H.sub.24N.sub.2S = 564.71) S-19 m/z = 574.2(C.sub.42H.sub.26N.sub.2O = 574.68) S-20 m/z = 564.17(C.sub.40H.sub.24N.sub.2S = 564.71) S-21 m/z = 564.17(C.sub.40H.sub.24N.sub.2S = 564.71) S-22 m/z = 813.31(C.sub.61H.sub.39N.sub.3 = 814) S-23 m/z = 696.26(C.sub.53H.sub.32N.sub.2 = 696.85) S-24 m/z = 691.23(C.sub.49H.sub.29N.sub.3O.sub.2 = 691.79) S-25 m/z = 710.27(C.sub.54H.sub.34N.sub.2 = 710.88) S-26 m/z = 610.24(C.sub.46H.sub.30N.sub.2 = 610.76) S-27 m/z = 670.15(C.sub.46H.sub.26N.sub.2S.sub.2 = 670.85) S-28 m/z = 640.29(C.sub.48H.sub.36N.sub.2 = 640.83) S-29 m/z = 598.2(C.sub.44H.sub.26N.sub.2O = 598.71) S-30 m/z = 623.24(C.sub.46H.sub.29N.sub.3 = 623.76) S-31 m/z = 458.18(C.sub.34H.sub.22N.sub.2 = 458.56) S-32 m/z = 548.19(C.sub.40H.sub.24N.sub.2O = 548.65) S-33 m/z = 508.19(C.sub.38H.sub.24N.sub.2 = 508.62) S-34 m/z = 508.19(C.sub.38H.sub.24N.sub.2 = 508.62) S-35 m/z = 623.24(C.sub.46H.sub.29N.sub.3 = 623.76) S-36 m/z = 564.17(C.sub.40H.sub.24N.sub.2S = 564.71) S-37 m/z = 627.2(C.sub.46H.sub.29NS = 627.81) S-38 m/z = 505.1(C.sub.34H.sub.19NS.sub.2 = 505.65) S-39 m/z = 514.15(C.sub.36H.sub.22N.sub.2S = 514.65) S-40 m/z = 575.17(C.sub.42H.sub.25NS = 575.73) S-41 m/z = 642.21(C.sub.46H.sub.30N.sub.2S = 642.82) S-42 m/z = 575.17(C.sub.42H.sub.25NS = 575.73) S-43 m/z = 606.18(C.sub.42H.sub.26N.sub.2OS = 606.74) S-44 m/z = 575.17(C.sub.42H.sub.25NS = 575.73) S-45 m/z = 551.17(C.sub.40H.sub.25NS = 551.71) S-46 m/z = 607.14(C.sub.42H.sub.25NS.sub.2 = 607.79) S-47 m/z = 525.16(C.sub.38H.sub.23NS = 525.67) S-48 m/z = 642.21(C.sub.46H.sub.30 N.sub.2S = 642.82) S-49 m/z = 548.19(C.sub.40H.sub.24N.sub.2O = 548.65) S-50 m/z = 473.14(C.sub.34H.sub.19NO.sub.2 = 473.53) S-51 m/z = 566.15(C.sub.39H.sub.22N.sub.2OS = 566.68) S-52 m/z = 459.16(C.sub.34H.sub.21NO = 459.55) S-53 m/z = 473.14(C.sub.34H.sub.19NO.sub.2 = 473.53) S-54 m/z = 523.16(C.sub.38H.sub.21NO.sub.2 = 523.59) S-55 m/z = 539.13(C.sub.38H.sub.21NOS = 539.65) S-56 m/z = 548.19(C.sub.40H.sub.24N.sub.2O = 548.65) S-57 m/z = 489.12(C.sub.34H.sub.19NOS = 489.59) S-58 m/z = 545.09(C.sub.36H.sub.19NOS.sub.2 = 545.67) S-59 m/z = 549.17(C.sub.40H.sub.23NO.sub.2 = 549.63) S-60 m/z = 565.15(C.sub.40H.sub.23NOS = 565.69) S-61 m/z = 523.16(C.sub.38H.sub.21NO.sub.2 = 523.59) S-62 m/z = 598.2(C.sub.44H.sub.26N.sub.2O = 598.71) S-63 m/z = 539.13(C.sub.38H.sub.21NOS = 539.65) S-64 m/z = 589.15(C.sub.42H.sub.23NOS = 589.71) S-65 m/z = 498.17(C.sub.36H.sub.22N.sub.2O = 498.59) S-66 m/z = 509.18(C.sub.38H.sub.23NO = 509.61) S-67 m/z = 548.19(C.sub.40H.sub.24N.sub.2O = 548.65) S-68 m/z = 549.17(C.sub.40H.sub.23NO.sub.2 = 549.63) S-69 m/z = 449.12(C.sub.32H.sub.19NS = 449.57) S-70 m/z = 439.1(C.sub.30H.sub.17NOS = 439.53) S-71 m/z = 647.22(C.sub.49H.sub.29NO = 647.78) S-72 m/z = 717.28(C.sub.52H.sub.35N.sub.3O = 717.87) S-73 m/z = 459.16(C.sub.34H.sub.21NO = 459.55) S-74 m/z = 533.18(C.sub.40H.sub.23NO = 533.63) S-75 m/z = 525.16(C.sub.38H.sub.23NS = 525.67) S-76 m/z = 564.17(C.sub.40H.sub.24N.sub.2S = 564.71) S-77 m/z = 575.19(C.sub.42H.sub.25NO.sub.2 = 575.67) S-78 m/z = 663.22(C.sub.49H.sub.29NO.sub.2 = 663.78) S-79 m/z = 647.22(C.sub.49H.sub.29NO = 647.78) S-80 m/z = 496.16(C.sub.36H.sub.20N.sub.2O = 496.57) S-81 m/z = 565.15(C.sub.40H.sub.23NOS = 565.69) S-82 m/z = 505.1(C.sub.34H.sub.19NS.sub.2 = 505.65) S-83 m/z = 765.25(C.sub.56H.sub.35NOSi = 765.99) S-84 m/z = 615.17(C.sub.44H.sub.25NOS = 615.75) S-85 m/z = 603.17(C.sub.43H.sub.25NOS = 603.74) S-86 m/z = 772.29(C.sub.59H.sub.36N.sub.2 = 772.95) S-87 m/z = 802.33(C.sub.61H.sub.42N.sub.2 = 803.02) S-88 m/z = 607.23(C.sub.47H.sub.29N = 607.76) S-89 m/z = 524.23(C.sub.39H.sub.28N.sub.2 = 524.67) S-90 m/z = 665.22(C.sub.49H.sub.31NS = 665.85) S-91 m/z = 633.25(C.sub.49H.sub.31N = 633.79) S-92 m/z = 775.29(C.sub.59H.sub.37NO = 775.95) S-93 m/z = 535.23(C.sub.41H.sub.29N = 535.69) S-94 m/z = 623.22(C.sub.47H.sub.29NO = 623.76) S-95 m/z = 687.2(C.sub.51H.sub.29NS = 687.86) S-96 m/z = 735.29(C.sub.57H.sub.37N = 735.93) S-97 m/z = 611.26(C.sub.47H.sub.33N = 611.79) S-98 m/z = 679.23(C.sub.50H.sub.33NS = 679.88) S-99 m/z = 787.32(C.sub.61H.sub.41N = 788.01) S-100 m/z = 743.33(C.sub.55H.sub.41N.sub.3 = 743.95) S-101 m/z = 485.21(C.sub.37H.sub.27N = 485.63) S-102 m/z = 471.2(C.sub.36H.sub.25N = 471.6) S-103 m/z = 571.19(C.sub.43H.sub.25NO = 571.68) S-104 m/z = 584.23(C.sub.44H.sub.28N.sub.2 = 584.72) S-105 m/z = 539.24(C.sub.40H.sub.21D.sub.5N.sub.2 = 539.69) S-106 m/z = 453.15(C.sub.32H.sub.15NS = 471.6) S-107 m/z = 563.26(C.sub.43H.sub.26D.sub.4NO = 563.74) S-108 m/z = 589.26(C.sub.44H.sub.23D.sub.5N.sub.2 = 584.72)
Element Data
[Example 1] Red Organic Light Emitting Device (Phosphorescent Host)
(255) An organic electroluminescent device was manufactured according to a conventional method by using the compound obtained through synthesis as a light emitting host material of the emitting layer. First, N1-(naphthalen-2-yl)-N4, N4-bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N1-phenylbenzene-1,4-diamine (hereinafter, 2-TNANA) film was vacuum-deposited on the ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm, and then on the hole injection layer, 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter, -NPB) as a hole transport compound was vacuum-deposited to a thickness of 60 nm to form a hole transport layer. Tris(4-(9H-carbazol-9-yl)phenyl)amine (hereinafter, TCTA) was vacuum-deposited to a thickness of 10 nm as an emitting auxiliary layer material on the hole transport layer to form a emitting auxiliary layer. After forming the emitting auxiliary layer, on the emitting auxiliary layer, the compound P-1 of the present invention represented by Formula 1 and the compound N-12 of the present invention represented by Formula (2) were used in a weight ratio (5:5) as a host, and an emitting layer was deposited to a thickness of 30 nm by doping (piq).sub.2r(acac) as a dopant material at a weight ratio of 95:5. Then, as a hole blocking layer, (1,1′-bisphenyl)-4-oleato)bis(2-methyl-8-quinolineoleato)aluminum (hereinafter, BAlq) was vacuum-deposited to a thickness of 10 nm, and as an electron transport layer, bis(10-hydroxybenzo[h]quinolinato)beryllium (hereinafter, BeBq.sub.2) was deposited to a thickness of 45 nm. Thereafter, LiF, which is an alkali metal halide, was deposited as an electron injection layer to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm and used as a cathode, thereby manufacturing an organic electroluminescent device.
[Example 2] to [Example 32]
(256) An organic electroluminescent device was manufactured in the same manner as in Example 1 by using the compounds of the present invention shown in Table 6 instead of the compounds P-1 and N-12 of the present invention as the host material of the emitting layer of Example 1.
[Comparative Example 1] to [Comparative Example 2]
(257) An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound A or Comparative Compound B was used instead of Compound P-1 of the present invention as a host material for the emitting layer.
(258) ##STR00154##
(259) The electroluminescence (EL) characteristics were measured with a PR-650 of a photo research company by applying a forward bias DC voltage to the organic electric devices manufactured in Examples and Comparative Examples prepared in this way, as a result of the measurement, the T95 lifespan was measured using a lifespan measuring device manufactured by McScience at a standard luminance of 2500 cd/m.sup.2. Table 6 shows the results of device fabrication and evaluation.
(260) TABLE-US-00007 TABLE 6 Current First Second Voltage Density Efficiency compound compound (V) (mA/cm.sup.2) (cd/A) T(95) Comp. Comp. Compound (N-12) 4.9 8.8 28.5 114.5 Example 1 Compound A Comp. Comp. Compound (N-12) 5.2 11.0 22.6 102.1 Example 2 Compound B Example 1 Compound (P-1) Compound (N-12) 4.8 8.1 30.8 123.8 Example 2 Compound (P-5) Compound (N-12) 4.8 8.1 31.0 125.0 Example 3 Compound (P-22) Compound (N-12) 4.7 7.9 31.6 123.3 Example 4 Compound (P-25) Compound (N-12) 4.7 8.3 30.1 129.1 Example 5 Compound (P-42) Compound (N-12) 4.7 7.9 31.7 129.4 Example 6 Compound (P-63) Compound (N-12) 4.7 7.7 32.5 127.4 Example 7 Compound (P-72) Compound (N-12) 4.7 7.6 32.8 125.5 Example 8 Compound (P-98) Compound (N-12) 4.7 7.8 32.1 125.1 Example 9 Compound (P-1) Compound (N-17) 4.6 7.7 32.4 131.0 Example 10 Compound (P-1) Compound (N-82) 4.7 8.0 31.1 129.4 Example 11 Compound (P-1) Compound (S-32) 4.7 7.8 32.1 136.9 Example 12 Compound (P-1) Compound (S-108) 4.6 7.5 33.4 139.9 Example 13 Compound (P-22) Compound (N-17) 4.5 7.5 33.2 129.8 Example 14 Compound (P-22) Compound (N-82) 4.6 7.8 31.9 127.4 Example 15 Compound (P-22) Compound (S-32) 4.6 7.6 32.8 134.7 Example 16 Compound (P-22) Compound (S-108) 4.5 7.3 34.1 138.7 Example 17 Compound (P-25) Compound (N-17) 4.5 7.9 31.6 136.7 Example 18 Compound (P-25) Compound (N-82) 4.6 8.3 30.3 134.3 Example 19 Compound (P-25) Compound (S-32) 4.6 8.0 31.2 141.7 Example 20 Compound (P-25) Compound (S-108) 4.5 7.7 32.5 146.2 Example 21 Compound (P-42) Compound (N-17) 4.5 7.5 33.4 136.7 Example 22 Compound (P-42) Compound (N-82) 4.6 7.8 32.0 134.3 Example 23 Compound (P-42) Compound (S-32) 4.7 7.6 32.9 141.6 Example 24 Compound (P-42) Compound (S-108) 4.6 7.3 34.2 145.7 Example 25 Compound (P-63) Compound (N-17) 4.4 7.3 34.2 135.3 Example 26 Compound (P-63) Compound (N-82) 4.5 7.6 32.8 133.2 example27 compound (P-63) compound (S-32) 4.6 7.4 33.8 140.5 example28 compound (P-63) compound (S-108) 4.5 7.1 35.1 144.4 example29 compound (P-98) compound (N-17) 4.5 7.4 33.9 133.2 example30 compound (P-98) compound (N-82) 4.5 7.7 32.5 130.6 example31 compound (P-98) compound (S-32) 4.6 7.5 33.5 138.0 example32 compound (P-98) compound (S-108) 4.5 7.2 34.7 141.9
(261) Referring to Table 6, when the compound of the present invention is used as the emitting layer material, it can be seen that the driving voltage is lowered and the efficiency and lifespan are improved compared to the case of using the comparative compound A or the comparative compound B.
(262) As can be seen above, when a host of the emitting layer is formed by mixing a plurality of compounds, the characteristics are different depending on the type of the first compound and the second compound, and when the same compound is applied to the second compound, the characteristic difference is remarkably displayed depending on the type of the first compound. Similarly, it shows a difference in driving voltage, efficiency, and lifespan according to the type of the second compound.
(263) Comparing Comparative Compound A and the compound of the present invention, Comparative Compound A and the compound of the present invention have similar structures, but the substituent of Comparative Compound A has a -p-phenyl-naphthyl structure, and the substituent of the compound of the present invention is -m-phenyl-naphthyl structure. Also, as can be seen in Table 6, when the compound of the present invention is applied to the element, it can be confirmed that the overall performance of the element is improved.
(264) Table 7 shows data measured using the DFT Method (B3LYP/6-31 g(D)) of the comparative compound A and the compound P-1 of the present invention by the Gaussian program.
(265) TABLE-US-00008 TABLE 7 G.HOMO G.LUMO G.BG G.S1 G.T1 Comparative −5.7084 −1.9862 3.7222 3.3427 2.403 compound A P-1 −5.673 −1.9682 3.7048 3.3016 2.3999
(266) As can be seen in Table 7, compared with Comparative Compound A, in compound P-1 of the present invention, T1 is similar, but the energy bandgap is decreased, and in particular, it can be confirmed that S1 is lowered. Due to this, the wavelength of the energy emitted from the host increases, and the energy is better transferred to the red dopant. In other words, the low S1 of the compound P-1 of the present invention facilitates the transfer of Foster energy to the dopant, so it seems to affect the overall performance improvement of the element.
(267) Although exemplary embodiments of the present invention have been described for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Therefore, the embodiment disclosed in the present invention is intended to illustrate the scope of the technical idea of the present invention, and the scope of the present invention is not limited by the embodiment. The scope of the present invention shall be construed on the basis of the accompanying claims, and it shall be construed that all of the technical ideas included within the scope equivalent to the claims belong to the present invention.