Compound and organic electroluminescent device using same

Abstract

The present invention relates to a novel compound and an organic electroluminescent device using same and, more specifically, to an organic compound having excellent electron transport ability, heat resistance, carrier transport ability, luminescence ability, and the like, and an organic electroluminescent device having improved characteristics such as luminescence efficiency, driving voltage, lifespan, and the like, due to including the organic compound in one or more organic material layers.

Description

Compounds and organic electroluminescent devices using the same

[0001] The present invention relates to a novel compound and an organic electroluminescent device using the same, and more particularly, to a compound having excellent electron transport capability and an organic electroluminescent device having improved characteristics such as luminous efficiency, driving voltage, and lifespan by including the compound in one or more organic layers.

[0002] In an organic electroluminescent device (hereinafter referred to as an "organic EL device"), when a voltage is applied between two electrodes, holes are injected into the organic layer from the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted. At this time, the materials used in the organic layer can be classified into light-emitting materials, hole-injecting materials, hole-transporting materials, electron-transporting materials, and electron-injecting materials, depending on their function.

[0003] Luminescent materials can be categorized into blue, green, and red luminescent materials based on their luminescent color, as well as yellow and orange luminescent materials for better natural color reproduction. Furthermore, host / dopant systems can be used as luminescent materials to enhance color purity and luminescence efficiency through energy transfer.

[0004] Dopant materials can be divided into fluorescent dopants, which utilize organic materials, and phosphorescent dopants, which utilize metal complexes containing heavy atoms such as Ir and Pt. The development of phosphorescent materials can theoretically improve luminescence efficiency by up to four times compared to fluorescent materials, and therefore, extensive research is being conducted not only on phosphorescent dopants but also on phosphorescent host materials.

[0005] Currently, NPB, BCP, Alq3, etc. are widely known as materials for hole injection layers, hole transport layers, hole blocking layers, and electron transport layers, and anthracene derivatives have been reported as materials for light-emitting layers. In particular, among light-emitting layer materials, metal complex compounds containing Ir, such as Firpic, Ir(ppy)3, and (acac)Ir(btp)2, which have advantages in terms of improving efficiency, are being used as phosphorescent dopant materials for blue, green, and red, and 4,4-dicarbazolybiphenyl (CBP) is being used as a phosphorescent host material.

[0006] However, while conventional organic layer materials offer advantages in terms of luminescence characteristics, their low glass transition temperatures and poor thermal stability make them unsatisfactory for the lifespan of organic electroluminescent devices. Therefore, the development of high-performance organic layer materials is urgently needed.

[0007] The present invention aims to provide a novel compound having excellent electron injection and transport ability, thermal stability, carrier transport ability, luminescence ability, etc., and which can be used as an organic layer material of an organic electroluminescent device, specifically, as a luminescent layer material, a life-span improving layer material, a luminescent auxiliary layer material, an electron transport layer material or an electron transport auxiliary layer material, and more specifically, as an electron transport layer material or an electron transport auxiliary layer material.

[0008] In addition, the present invention seeks to provide an organic electroluminescent device having a low driving voltage, high luminous efficiency, excellent electrical stability, and improved lifespan, including the novel compound.

[0009] To achieve the above purpose, the present invention provides a compound represented by the following chemical formula 1:

[0010]

[0011] (In the above chemical formula 1,

[0012] X1 to X4 are the same or different, and are each independently N or C(Ar1), provided that at least two of X1 to X4 are N;

[0013] Y1 is selected from the group consisting of O, S, Se, C(Ar2)(Ar3) and N(Ar4),

[0014] a is 1 or 2,

[0015] b is an integer from 0 to 4,

[0016] R1, R2, and Ar1 to Ar4 are the same or different from each other, and each independently represents hydrogen, deuterium (D), a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, C1 to C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 A cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of, heteroaryl group of 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 is selected from the group consisting of arylamine groups;

[0017] n is an integer from 1 to 4,

[0018] L1 is C6~C 18 is an arylene group,

[0019] The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group and arylamine group of the above R1, R2, and Ar1 to Ar4, and the arylene group of the above L1 are each independently deuterium (D), halogen, cyano group, nitro group, amino group, hydroxy group, C1 to C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 (Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, and when there are multiple substituents, they are the same or different from each other).

[0020] In addition, the present invention provides an organic electroluminescent device comprising an anode; a cathode; and one or more organic layers interposed between the anode and the cathode, wherein at least one of the one or more organic layers comprises a compound represented by the aforementioned chemical formula 1.

[0021] In one example, the organic layer containing the compound may be an electron transport layer or an electron transport auxiliary layer.

[0022] Since the compound of the present invention has excellent electron transport ability, electrochemical stability, thermal stability, etc., it can be used as an organic layer material of an organic electroluminescent device. In particular, when the compound of the present invention is used as an electron transport layer material or an electron transport auxiliary layer material, it is possible to manufacture an organic electroluminescent device having superior luminescence performance, low driving voltage, high efficiency, and long lifespan characteristics compared to conventional materials, and further, a full-color display panel with improved performance and lifespan can also be manufactured.

[0023] The effects according to the present invention are not limited to those exemplified above, and more diverse effects are included in this specification.

[0024] FIG. 1 is a cross-sectional view schematically showing an organic electroluminescent device according to a first embodiment of the present invention.

[0025] FIG. 2 is a cross-sectional view schematically showing an organic electroluminescent device according to a second embodiment of the present invention.

[0026] FIG. 3 is a cross-sectional view schematically showing an organic electroluminescent device according to a third embodiment of the present invention.

[0027] <Explanation of symbols>

[0028] 100: anode, 200: cathode,

[0029] 300: Organic layer, 310: Hole injection layer,

[0030] 320: hole transport layer, 330: light emitting layer,

[0031] 340: electron transport layer, 350: electron injection layer,

[0032] 360: Electron transport auxiliary layer

[0033] Hereinafter, the present invention will be described.

[0034] <New organic compounds>

[0035] The compound according to the present invention comprises a fused heteroaromatic ring moiety in which a single-ring nitrogen-containing heteroaromatic ring and a benzoic ring are fused; and a spiro[cyclohexane-1,9'-fluorene] moiety bonded to the fused heteroaromatic ring moiety via a linker group (e.g., an arylene group), wherein a cyano group (-CN) is introduced into one benzene ring of the spiro[cyclohexane-1,9'-fluorene] moiety, and is represented by the above chemical formula 1. The compound of the present invention represented by the above chemical formula 1 has excellent electron injection and transport ability, electrochemical stability, heat resistance, etc., and can be used as an electron transport layer material or an electron transport auxiliary layer material that can improve high efficiency, long life, and driving voltage characteristics of an organic electroluminescent device.

[0036] In the compound according to the present invention, the fused heteroaromatic ring moiety is an electron withdrawing group (EWG) with strong electron absorption in its molecular structure due to the condensation of a monocyclic nitrogen-containing heteroaromatic ring and a benzoic ring, and thus can improve electron injection and transport properties. Since this fused heteroaromatic ring moiety has a wider conjugation area than a monocyclic azine group (e.g., pyridine group, pyrimidine group, triazine group) or a quinoline group, more electrons can be distributed in the fused heteroaromatic ring moiety, and therefore, the compound of the present invention has excellent initial operating voltage and total charge transport capacity. In addition, since the condensed heteroaromatic ring moiety has an expanded ET moiety region compared to a monocyclic azine group or a quinoline group, the compound of the present invention has better electrical properties in a wider and flatter region, thereby having a stronger ET power (Electronic Power), which can realize low operating voltage and high efficiency of the device. Here, the ET power (Electronic Power) is that the flatter the structure of the compound, the easier the movement of electrons within the molecule, increasing electron mobility, and thus facilitating electron injection. In addition, the stronger the EWG is substituted, the lower the LUMO, making it easier for electrons to hop to the neighboring level, and the stronger the ET power, the lower the LUMO, facilitating electron movement. Therefore, the compound of the present invention can secure long-life characteristics of the device due to the structural stability resulting from the flat structure. In particular, the present invention can maximize the lifespan characteristics of a device by bonding a spiro[cyclohexane-1,9'-fluorene] moiety to a condensed heteroaromatic ring moiety, thereby demonstrating strength in devices with large areas.

[0037] In addition, in the compound of the present invention, the condensed heteroaromatic ring moiety has more electrons than a typical dibenzofuran group or dibenzothiophene group, and thus can perform the role of an EWG, thereby improving the electron injection and transport properties of the compound. Therefore, when the compound of the present invention is applied to an electron transport layer or an electron transport auxiliary layer of an organic electroluminescent device, the operating voltage as well as the current efficiency of the device can be improved.

[0038] In addition, in the compound of the present invention, by designing the structure to increase the dipole moment by substituting a cyano group (-CN) on one benzene ring of the spiro[cyclohexane-1,9'-fluorene] moiety, the interaction with the adjacent cathode is improved, so that a larger amount of electrons can be obtained from the cathode and transported to the light-emitting layer, and also the initial electron generation can be improved. Therefore, the compound of the present invention can improve the initial driving voltage and luminous efficiency of the device. In addition, since the compound of the present invention has an increased dipole moment due to the substituted cyano group, the stacking between the electrode and the organic material can be increased, thereby minimizing defects within the device.

[0039] In addition, in the compound according to the present invention, a fused heteroaromatic ring moiety and a spiro[cyclohexane-1,9'-fluorene] moiety are connected via an arylene group (e.g., a monocyclic arylene group or a fused or non-fused 2-4 ring arylene group) as a linker group. Accordingly, the spiro[cyclohexane-1,9'-fluorene] moiety, which is an electron donating group (EDG) with high electron donating ability, and the fused heteroaromatic ring moiety, which is an electron withdrawing group (EWG) with high electron absorbing ability, are separated on both sides in the molecular structure, thereby exerting a separation effect of LUMO - HOMO orbitals, thereby improving the bandgap, and thus the compound of the present invention can have an appropriate LUMO energy. Therefore, the compound of the present invention can lower the operating voltage of the device and increase the current efficiency compared to a compound in which a condensed heteroaromatic ring moiety and a spiro[cyclohexane-1,9'-fluorene] moiety are directly bonded without a linker group. In addition, the compound of the present invention can improve the characteristics of the device by having thermal stability, high glass transition temperature characteristics, and uniform morphology.

[0040] In addition, since the compound represented by Chemical Formula 1 of the present invention has a high triplet energy, it can prevent excitons generated in the light-emitting layer from diffusing (moving) to the adjacent electron transport layer or hole transport layer. Therefore, the number of excitons contributing to light emission in the light-emitting layer increases, so that the light-emitting efficiency of the device can be improved, and the durability and stability of the device can be improved, so that the lifespan of the device can be efficiently increased. Most of the developed materials exhibit physical characteristics that allow for low-voltage operation, thereby improving the lifespan.

[0041] As described above, the compound represented by the chemical formula 1 of the present invention has excellent electron transport ability, thermal stability, electrochemical stability, etc. Therefore, the compound of the present invention can be used as an organic layer material of an organic electroluminescent device, preferably an emitting layer material (a blue, green, and / or red phosphorescent host material), an electron transport layer / injection layer material, a hole transport layer / injection layer material, an emitting auxiliary layer material, a life-span improving layer material, an electron transport auxiliary layer material, and more preferably an electron transport layer material or an electron transport auxiliary layer material. An organic electroluminescent device including the compound of the present invention can have greatly improved performance and life-span characteristics, and a full-color organic light-emitting panel to which such an organic electroluminescent device is applied can also have its performance maximized.

[0042]

[0043] In the compound represented by chemical formula 1 according to the present invention, a spiro[cyclohexane-1,9'-fluorene] moiety having a cyano group (-CN) introduced therein and a condensed heteroaromatic ring moiety have a basic skeleton bonded via a linker group (e.g., an arylene group).

[0044] The above spiro[cyclohexane-1,9'-fluorene] moiety can be embodied as one selected from the group consisting of the following moieties CF1 to CF4 depending on the bonding position with the linker.

[0045]

[0046] Depending on the bonding position of the spiro[cyclohexane-1,9'-fluorene] moiety and the linker, and the bonding position of the condensed heteroaromatic ring moiety and the linker, the compound represented by the above chemical formula 1 may be a compound represented by any one of the following chemical formulas 2 to 9. However, the present invention is not limited thereto.

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] In the above chemical formulas 2 to 9,

[0056] X1 to X4, Y1, a, b, R1, R2, n and L1 are each as defined in the above chemical formula 1,

[0057] b1 is an integer from 0 to 3, specifically 0 or 1.

[0058] In the chemical formula 1 according to the present invention, the fused heteroaromatic ring moiety is a polycyclic nitrogen-containing heteroaromatic ring moiety in which a single-ring nitrogen-containing heteroaromatic ring (e.g., a pyrimidine ring, a triazine ring, a pyridazine ring) and a benzoic ring (e.g., a benzofuran ring, a benzothiophene ring, an indole ring, an indene ring, etc.) are fused, and is a type of electron-withdrawing group (EWG) with excellent electron transport ability.

[0059] In such condensed heteroaromatic ring moieties, X1 to X4 are the same or different from each other, and are each independently N or C(Ar1), provided that at least two of X1 to X4 are N, and preferably two of X1 to X4 may be N. In this case, any carbon of C(Ar1) other than N may be connected to L1.

[0060] Additionally, Y1 is selected from the group consisting of O, S, Se, C(Ar2)(Ar3) and N(Ar4), and may be specifically O or S.

[0061] For example, a fused heteroaromatic ring moiety ( The moiety) may be selected from the group consisting of the moieties Mo1-1 to Mo1-34 below, according to the aforementioned X1 to X4, and specifically may be selected from the group consisting of the moieties Mo1-1 to Mo1-18, and Mo1-23 to Mo1-34 below. However, the present invention is not limited thereto.

[0062]

[0063]

[0064]

[0065] In the above moieties Mo1-1 to Mo1-34,

[0066] Y1, b, R1 and R2 are each as defined in the above chemical formula 1,

[0067] b1 is an integer from 0 to 3, specifically 0 or 1.

[0068] In the chemical formula 1 according to the present invention, Ar1 to Ar4 are the same or different from each other, and each independently represents hydrogen, deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxyl group (-OH), C1 to C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 A cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of, heteroaryl group of 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60Arylphosphine oxide group and C6~C 60 Selected from the group consisting of arylamine groups, or condensed with adjacent groups (e.g., Ar1-R1, Ar2-Ar3, etc.) to form a condensed ring, specifically hydrogen, C1~C 40 Alkyl group of C6~C 60 It is selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, or can be condensed with an adjacent group (e.g., Ar1-R1, Ar2-Ar3, etc.) to form a condensed ring. Here, the condensed ring is C3~C 60 Condensed aliphatic rings (specifically, C3~C 30 condensed aliphatic ring), C6~C 60 Condensed aromatic rings (specifically, C6~C 30 fused aromatic ring), fused heteroaromatic ring having 5 to 60 members (specifically, fused heteroaromatic ring having 5 to 30 members), C3 to C 60 It may be at least one selected from the group consisting of spiro rings and combinations thereof.

[0069] The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group, arylamine group and condensed ring of the above Ar1 to Ar4 are each independently deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxy group (-OH), C1 to C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, specifically deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxy group (-OH), C1~C 40 Alkyl group of C6~C 60 An aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C6~C 60 Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, more specifically deuterium (D), C1~C 20 Alkyl group of C6~C 30 An aryl group, a heteroaryl group having 5 to 30 nuclear atoms, and a C6~C 30 It may be substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups. In this case, when there are multiple substituents, they may be the same or different from each other.

[0070] In the chemical formula 1 according to the present invention, a is 1 or 2, and specifically, may be 1. At this time, a+b≤5. Here, when a is 1 or 2, it means that hydrogen is substituted with a substituent (R1), and at this time, when there are multiple R1s, the multiple R1s are the same or different from each other.

[0071] R1 is hydrogen, deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxyl group (-OH), C1~C 40 Alkyl group of C2~C 40Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 A cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of, heteroaryl group of 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 Selected from the group consisting of arylamine groups, specifically C6~C 60 It can be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and more specifically, C6~C 30 It can be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 30 nuclear atoms.

[0072] For example, R1 may be selected from the group consisting of a phenyl group, a biphenyl group, a terphenyl group, and a naphthyl group, and may specifically be a phenyl group or a naphthyl group.

[0073] The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group and arylamine group of the above R1 and the arylene group of the above L1 are each independently deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxy group (-OH), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, specifically deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxy group (-OH), C1~C 40 Alkyl group of C6~C 60 An aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C6~C 60 Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, more specifically deuterium (D), C1~C 20 Alkyl group of C6~C 30 An aryl group, a heteroaryl group having 5 to 30 nuclear atoms, and a C6~C 30 It may be substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups. In this case, when there are multiple substituents, they may be the same or different from each other.

[0074] In chemical formula 1 according to the present invention, b is an integer from 0 to 4, and can be specifically 0 or 1.

[0075] Here, when b is 0, it means that hydrogen is not substituted with a substituent (R2). On the other hand, when b is an integer from 1 to 4, it means that hydrogen is substituted with a substituent (R2). In this case, when R2 is plural, the plural R1s are the same or different from each other.

[0076] R2 is hydrogen, deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxyl group (-OH), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 A cycloalkyl group, a heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of, heteroaryl group of 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 Selected from the group consisting of arylamine groups, specifically C6~C 60 It can be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, and more specifically, C6~C 30 It can be selected from the group consisting of an aryl group and a heteroaryl group having 5 to 30 nuclear atoms.

[0077] The alkyl group, alkenyl group, alkynyl group, cycloalkyl group, heterocycloalkyl group, aryl group, heteroaryl group, alkyloxy group, aryloxy group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group and arylamine group of the above R2 and the arylene group of the above L1 are each independently deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxy group (-OH), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, specifically deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxy group (-OH), C1~C 40 Alkyl group of C6~C 60 An aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C6~C 60 Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, more specifically deuterium (D), C1~C 20 Alkyl group of C6~C 30An aryl group, a heteroaryl group having 5 to 30 nuclear atoms, and a C6~C 30 It may be substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups. In this case, when there are multiple substituents, they may be the same or different from each other.

[0078] In the chemical formula 1 according to the present invention, n is an integer from 1 to 4. Here, when n is an integer from 1 to 4, L1 is a divalent linker group, C6~C 18 is an arylene group. Here, multiple L1s may be the same or different from each other.

[0079] For example, L1 may be a monocyclic arylene group, or a fused or non-fused arylene group having 2 to 4 rings.

[0080] The arylene group of the above L1 is deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxyl group (-OH), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, specifically deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxy group (-OH), C1~C 40 Alkyl group of C6~C 60 An aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C6~C 60 Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, more specifically deuterium (D), C1~C 20 Alkyl group of C6~C 30 An aryl group, a heteroaryl group having 5 to 30 nuclear atoms, and a C6~C 30 It may be substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups. In this case, when there are multiple substituents, they may be the same or different from each other.

[0081] For example, L1 may be selected from the group consisting of linker groups L1-1 to L1-11, wherein multiple L1s may be the same or different from each other. However, the present invention is not limited thereto.

[0082]

[0083] In the above linker groups L1-1 to L1-11,

[0084] c is an integer from 0 to 4, specifically an integer from 0 to 2,

[0085] d is an integer from 0 to 6, specifically an integer from 0 to 2,

[0086] e is an integer from 0 to 8, specifically an integer from 0 to 2,

[0087] f is an integer from 0 to 7, specifically an integer from 0 to 2,

[0088] g is an integer from 0 to 3, specifically an integer from 0 to 2,

[0089] h is an integer from 0 to 5, specifically an integer from 0 to 2,

[0090] i is an integer from 0 to 10, specifically an integer from 0 to 2,

[0091] Multiple R's are the same or different from each other,

[0092] R is deuterium (D), halogen (e.g., -F, -Cl, -Br, -I, etc.), cyano group (-CN), nitro group (-NO2), amino group (-NH2), hydroxyl group (-OH), C1~C 40 Alkyl group of C2~C 40 Alkenyl group, C2~C 40 Alkynyl group, C3~C 40 Cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C6~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C1~C 40 Alkyloxy group, C6~C 60 Aryloxy group of C1~C 40 Alkylsilyl group, C6~C 60 Arylsilyl group, C1~C 40 Alkyl boron group, C6~C 60 Aryl boron group, C6~C 60 Arylphosphine group, C6~C 60 Arylphosphine oxide group and C6~C 60 It may be selected from the group consisting of arylamine groups, specifically deuterium (D), cyano group (-CN), C1~C 20 Alkyl group of C6~C 30 An aryl group, a heteroaryl group having 5 to 30 nuclear atoms, and a C6~C 30 It may be selected from the group consisting of arylamine groups.

[0093] According to the aforementioned L1, the compound represented by the above chemical formula 1 may be a compound represented by the following chemical formula 10 or 11. However, it is not limited thereto.

[0094]

[0095]

[0096] In the above chemical formulas 10 and 11,

[0097] X1 to X4, Y, a, b, R1, and R2 are each as defined in the above chemical formula 1,

[0098] b1 is an integer from 0 to 3, specifically 0 or 1.

[0099] According to the aforementioned condensed heteroaromatic ring moiety and L1, the compound represented by the above chemical formula 1 may be a compound represented by any one of the following chemical formulas 12 to 15. However, the present invention is not limited thereto.

[0100]

[0101]

[0102]

[0103]

[0104] In the above chemical formulas 12 to 15,

[0105] Y1, b, R2, and n are each as defined in the above chemical formula 1,

[0106] Multiple R1s are identical or different from each other,

[0107] R1 is C6~C 60 Selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms,

[0108] The aryl group and heteroaryl group of the above R1 are each independently deuterium (D), halogen, cyano group, nitro group, amino group, hydroxy group, C1~C 40 Alkyl group of C6~C 60 An aryl group, a heteroaryl group having 5 to 60 nuclear atoms, and a C6~C 60is substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, and when there are multiple substituents, they are the same or different from each other,

[0109] b1 is an integer from 0 to 3, specifically 0 or 1.

[0110] The compound represented by the chemical formula 1 of the present invention described above can be further specified as the following compounds, but is not limited thereto.

[0111]

[0112]

[0113]

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128]

[0129] In the present invention, "alkyl" means a monovalent substituent derived from a straight or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc.

[0130] In the present invention, "alkenyl" means a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and at least one carbon-carbon double bond. Examples thereof include, but are not limited to, vinyl, allyl, isopropenyl, and 2-butenyl.

[0131] In the present invention, "alkynyl" means a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and at least one carbon-carbon triple bond. Examples thereof include, but are not limited to, ethynyl and 2-propynyl.

[0132] In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

[0133] In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, wherein at least one carbon atom, preferably 1 to 3 carbons in the ring, is substituted with a heteroatom such as N, O, S or Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine. Here, the number of nuclear atoms means the number of atoms forming the ring, i.e., the number of ring atoms.

[0134] In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, which is a single ring or a combination of two or more rings. Furthermore, a form in which two or more rings are simply attached to each other (pendant) or condensed may also be included. Examples of such aryls include, but are not limited to, phenyl, naphthyl, phenanthryl, and anthryl.

[0135] In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 60 nuclear atoms. At this time, at least one carbon atom in the ring, preferably 1 to 3 carbon atom, is substituted with a heteroatom such as N, O, S, or Se. In addition, a form in which two or more rings are simply attached to each other (pendant) or condensed may be included, and a form condensed with an aryl group may also be included. Examples of such heteroaryls include, but are not limited to, 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl; polycyclic rings such as phenoxathienyl, indolizinyl, indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl, 2-pyridinyl, and 2-pyrimidinyl. Here, the number of nuclear atoms means the number of atoms forming the ring, i.e., the number of ring atoms.

[0136] In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means alkyl having 1 to 40 carbon atoms, and may include a linear, branched, or cyclic structure. Examples of such alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, and pentoxy.

[0137] In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, and diphenyloxy.

[0138] In the present invention, “alkylsilyl” means silyl substituted with alkyl having 1 to 40 carbon atoms, and includes not only mono- but also di- and tri-alkylsilyl.

[0139] In addition, "arylsilyl" means silyl substituted with aryl having 5 to 60 carbon atoms, and includes polyarylsilyl such as mono-, di-, and tri-arylsilyl.

[0140] In the present invention, “alkylboron group” means a boron group substituted with an alkyl having 1 to 40 carbon atoms, and “arylboron group” means a boron group substituted with an aryl having 6 to 60 carbon atoms.

[0141] In the present invention, “alkylphosphinyl group” means a phosphine group substituted with an alkyl having 1 to 40 carbon atoms, and includes mono- as well as di-alkylphosphinyl groups.

[0142] In addition, in the present invention, “arylphosphinyl group” means a phosphine group substituted with an aryl having 6 to 60 carbon atoms, and includes not only mono- but also di-arylphosphinyl groups.

[0143] In the present invention, “arylphosphine oxide group” means a phosphine oxide group substituted with an aryl having 6 to 60 carbon atoms, and includes not only mono- but also di-arylphosphine oxide groups.

[0144] In the present invention, “arylamine” means an amine substituted with an aryl having 6 to 60 carbon atoms, and includes not only mono- but also di-arylamine.

[0145] In the present invention, the "condensed ring" is a condensed aliphatic ring having 3 to 40 carbon atoms, a condensed aromatic ring having 6 to 60 carbon atoms, a condensed heteroaliphatic ring having 3 to 60 nuclear atoms, a condensed heteroaromatic ring having 5 to 60 nuclear atoms, C3~C 60 It means a spyro ring or a combination thereof. Here, the nuclear atomic number means the number of atoms forming the ring, i.e. the number of ring atoms.

[0146]

[0147] Organic electroluminescent devices

[0148] Meanwhile, the present invention provides an organic electroluminescent device (hereinafter, 'organic EL device') comprising a compound represented by the above-described chemical formula 1.

[0149] Specifically, the organic electroluminescent device according to the present invention includes an anode (100), a cathode (200), and one or more organic layers (300) interposed between the anode and the cathode, as illustrated in FIGS. 1 to 3, and at least one of the one or more organic layers includes a compound represented by the chemical formula 1. At this time, the compound may be used alone, or two or more may be mixed and used.

[0150] The organic layer (300) of one or more layers above may include at least one of a hole injection layer (310), a hole transport layer (320), a light emitting layer (330), an electron transport layer (340), and an electron injection layer (350), and optionally may additionally include at least one of an electron transport auxiliary layer (360) and a hole transport auxiliary layer (not shown). At this time, at least one organic layer (300) includes a compound represented by the chemical formula 1. Specifically, the organic layer including the compound of the chemical formula 1 may be an electron transport layer (340) or an electron transport auxiliary layer (360).

[0151] According to an example, the organic layer of one or more layers may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and may optionally further include at least one of an electron transport auxiliary layer and a hole transport auxiliary layer. The electron transport layer includes a compound represented by the above chemical formula 1. In this case, the compound represented by the above chemical formula 1 is included in the organic electroluminescent device as an electron transport layer material. In such an organic electroluminescent device, electrons can be easily injected from the cathode or the electron injection layer to the electron transport layer due to the compound of the above chemical formula 1, and can also move quickly from the electron transport layer to the light emitting layer, so that the binding force between holes and electrons in the light emitting layer is high. Therefore, the organic electroluminescent device of the present invention is excellent in luminous efficiency, power efficiency, brightness, etc. In addition, the compound of the above chemical formula 1 has excellent thermal stability and electrochemical stability, and can improve the performance of the organic electroluminescent device.

[0152] The compound of chemical formula 1 may be used alone or in combination with an electron transport layer material known in the art.

[0153] In the present invention, the electron transport layer material that can be mixed with the compound of the above chemical formula 1 may be an electron transport material or n-type dopant commonly known in the art. Non-limiting examples of the electron transport material that can be used in the present invention include oxazole compounds, isoxazole compounds, triazole compounds, isothiazole compounds, oxadiazole compounds, thiadiazole compounds, perylene compounds, and aluminum complexes (e.g., Alq). 3,tris(8-quinolinolato)-aluminium), gallium complexes (e.g., Gaq'2OPiv, Gaq'2OAc, 2(Gaq'2)), etc. These may be used alone or in combination of two or more. Examples of n-type dopants usable in the present invention may be metals (e.g., alkali metals or alkaline earth metals) or complexes of the above metals, and specifically, may be LiQ (Lithium Quinolate), etc.

[0154] In the present invention, when the compound of the above chemical formula 1 and the electron transport layer material are mixed, the mixing ratio thereof is not particularly limited and can be appropriately controlled within a range known in the art.

[0155] According to another example, the organic layer of one or more layers includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport auxiliary layer, an electron transport layer, and an electron injection layer, and the electron transport auxiliary layer includes a compound represented by the chemical formula 1. In this case, the compound represented by the chemical formula 1 is included in the organic electroluminescent device as an electron transport auxiliary layer material. The compound represented by the chemical formula 1 has a high triplet energy. Therefore, when the compound of the chemical formula 1 is included as an electron transport auxiliary layer material, the efficiency of the organic electroluminescent device can be increased due to the TTF (triplet-triplet fusion) effect. In addition, the compound of the chemical formula 1 can prevent excitons or holes generated in the light emitting layer from diffusing to the electron transport layer adjacent to the light emitting layer. Therefore, the number of excitons contributing to light emission in the light emitting layer increases, so that the light emitting efficiency of the device can be improved, and the durability and stability of the device can be improved, so that the lifespan of the device can be efficiently increased.

[0156] The compound of chemical formula 1 may be used alone or in combination with an electron transport layer auxiliary layer material known in the art.

[0157] In the present invention, the electron transport auxiliary layer material that can be mixed with the compound of the above chemical formula 1 includes electron transport materials commonly known in the art, such as oxadiazole derivatives, triazole derivatives, phenanthroline derivatives (e.g., BCP), and heterocyclic derivatives containing nitrogen, but is not limited thereto.

[0158] The structure of the organic electroluminescent device of the present invention described above is not particularly limited, but for example, an anode (100), one or more organic layers (300), and a cathode (200) may be sequentially laminated on a substrate (see FIGS. 1 to 3). In addition, although not shown, it may have a structure in which an insulating layer or an adhesive layer is inserted at the interface between the electrode and the organic layer.

[0159] According to an example, the organic electroluminescent device may have a structure in which an anode (100), a hole injection layer (310), a hole transport layer (320), a light-emitting layer (330), an electron transport layer (340), and a cathode (200) are sequentially laminated on a substrate, as illustrated in FIG. 1. Optionally, as illustrated in FIG. 2, an electron injection layer (350) may be positioned between the electron transport layer (340) and the cathode (200). In addition, an electron transport auxiliary layer (360) may be positioned between the light-emitting layer (330) and the electron transport layer (340) (see FIG. 3).

[0160] The organic electroluminescent device of the present invention can be manufactured by forming the organic layer and electrode using materials and methods known in the art, except that at least one of the organic layers (300) [e.g., the electron transport layer (340)] includes a compound represented by the chemical formula 1.

[0161] The above organic layer can be formed by vacuum deposition or solution coating. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

[0162] The substrate usable in the present invention is not particularly limited, and non-limiting examples include silicon wafers, quartz, glass plates, metal plates, plastic films and sheets, etc.

[0163] Examples of anode materials include, but are not limited to, metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO2:Sb; conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDT), polypyrrole, or polyaniline; and carbon black.

[0164] Examples of cathode materials include, but are not limited to, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver (Ag), tin, or lead, or alloys thereof; and multilayered materials such as LiF / Al or LiO2 / Al.

[0165] In addition, the hole injection layer, hole transport layer, light emitting layer, electron injection layer, and hole transport auxiliary layer are not particularly limited, and conventional materials known in the art can be used.

[0166]

[0167] Hereinafter, the present invention will be described in detail through examples. However, the following examples are only illustrative of the present invention, and the present invention is not limited to the following examples.

[0168] [Synthesis Example 1] Synthesis of Compound 1-1

[0169]

[0170] [Synthesis Example 1-1] Synthesis of Compound 1-1-ii

[0171] 100g (418.3mmol, 1eq) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 61.2g (502.0mmol, 1.2eq) of phenylboronic acid, 419.3g (16.7mmol, 0.04eq) of Pd(PPh3), and 115.6g (836.6mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-1-ii (2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine) (103.3 g, yield 88%).

[0172] Mass: [(M+H) + ] : 280.71

[0173] NMR( 1 H): σ= 7.84(2H, d), 7.70-7.65(2H, m), 7.53-7.49(3H, m), 7.36(1H, t), 7.22(1H, t)

[0174] [Synthesis Example 1-2] Synthesis of Compound 1-1-i

[0175] 103.3g (368.1mmol, 1eq) of 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine, (2-chlorophenyl)boronic acid 63.3g (404.9mmol, 1.1eq), Pd(PPh3) 412.8g (11.0mmol, 0.03eq), and K2CO3 101.8g (736.2mmol, 2eq) were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-1-I (2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine) (118.2 g, yield 90%).

[0176] Mass: [(M+H) + ] : 356.81

[0177] NMR( 1 H): σ= 7.84(2H, d) 7.70-7.53(8H,m), 7.387.36(3H, m), 7.22(1H, t)

[0178] [Synthesis Example 1-3] Synthesis of Compound 1-1

[0179] 20g (56.1mmol, 1eq) of 2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine, 25.9g (67.3mmol, 1.2eq) of 7'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, 0.4g (1.7mmol, 0.03eq) of Pd(OAc), 2.7g (5.6mmol, 0.1eq) of XPhos, and 18.6g (134.5mmol, 2eq) of K2CO3 were added to 300ml of toluene, 80ml of EtOH, and 80ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-1 (7'-(2-(4-phenylbenzofuro[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile)(26.0 g, yield 80%).

[0180] Mass: [(M+H) + ] : 579.70

[0181]

[0182] [Synthesis Examples 2 to 9]

[0183] The target compound C was synthesized in the same manner as in Synthesis Example 1, except that intermediates A and B described in Table 1 below were used, respectively.

[0184]

[0185]

[0186]

[0187] [Synthesis Example 10] Synthesis of Compound 1-2

[0188]

[0189] [Synthesis Example 10-1] Synthesis of Compound 1-2-ii

[0190] 100g (418.3mmol, 1eq) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 61.2g (502.0mmol, 1.2eq) of phenylboronic acid, 419.3g (16.7mmol, 0.04eq) of Pd(PPh3), and 115.6g (836.6mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-2-ii (2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine) (103.3 g, yield 88%).

[0191] Mass: [(M+H) + ] : 280.71

[0192] NMR( 1 H): σ= 7.84(2H, d), 7.70-7.65(2H, m), 7.53-7.49(3H, m), 7.36(1H, t), 7.22(1H, t)

[0193] [Synthesis Example 10-2] Synthesis of Compound 1-2-i

[0194] 103.3 g (368.1 mmol, 1 eq) of 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine, 63.3 g (404.9 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 412.8 g (11.0 mmol, 0.03 eq) of Pd(PPh3), and 101.8 g (736.2 mmol, 2 eq) of K2CO3 were added to 1500 ml of THF and 500 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-2-i (2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine) (118.2 g, yield 90%).

[0195] Mass: [(M+H) + ] : 356.81

[0196] NMR( 1 H): σ= 7.84(2H, d) 7.70-7.53(8H,m), 7.387.36(3H, m), 7.22(1H, t)

[0197] [Synthesis Example 10-3] Synthesis of Compound 1-2

[0198] 20 g (56.1 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine, 25.9 g (67.3 mmol, 1.2 eq) of 6'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, 0.4 g (1.7 mmol, 0.03 eq) of Pd(OAc), 2.7 g (5.6 mmol, 0.1 eq) of XPhos, and 18.6 g (134.5 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-2 {2'-(2-(4-phenylbenzofuro[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-6'-carbonitrile} (24.4 g, yield 75%).

[0199] Mass: [(M+H) + ] : 579.70

[0200]

[0201] [Synthesis Examples 11 to 17]

[0202] The target compound C was synthesized in the same manner as in Synthesis Example 10, except that intermediates A and B described in Table 2 below were used, respectively.

[0203]

[0204]

[0205]

[0206] [Synthesis Example 18] Synthesis of Compound 1-3

[0207]

[0208] [Synthesis Example 18-1] Synthesis of Compound 1-3-ii

[0209] 100g (418.3mmol, 1eq) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 61.2g (502.0mmol, 1.2eq) of phenylboronic acid, 419.3g (16.7mmol, 0.04eq) of Pd(PPh3), and 115.6g (836.6mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-3-ii (2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine) (103.3 g, yield 88%).

[0210] Mass: [(M+H) + ] : 280.71

[0211] NMR( 1 H): σ= 7.84(2H, d), 7.70-7.65(2H, m), 7.53-7.49(3H, m), 7.36(1H, t), 7.22(1H, t)

[0212] [Synthesis Example 18-2] Synthesis of Compound 1-3-i

[0213] 103.3 g (368.1 mmol, 1 eq) of 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine, 63.3 g (404.9 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 12.8 g (11.0 mmol, 0.03 eq) of Pd(PPh3)4, and 101.8 g (736.2 mmol, 2 eq) of K2CO3 were added to 1500 ml of THF and 500 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 1-3-i, 2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine (118.2 g, yield 90%).

[0214] Mass: [(M+H) + ] : 356.81

[0215] NMR( 1 H): σ= 7.84(2H, d) 7.70-7.53(8H,m), 7.387.36(3H, m), 7.22(1H, t)

[0216] [Synthesis Example 18-3] Synthesis of Compound 1-3

[0217] 20 g (56.1 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine, 25.9 g (67.3 mmol, 1.2 eq) of 2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-5'-carbonitrile, 0.4 g (1.7 mmol, 0.03 eq) of Pd(OAc), 2.7 g (5.6 mmol, 0.1 eq) of XPhos, and 18.6 g (134.5 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-3 {2'-(2-(4-phenylbenzofuro[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-5'-carbonitrile} (22.7 g, yield 70%).

[0218] Mass: [(M+H) + ] : 579.70

[0219]

[0220] [Synthesis Examples 19 and 20]

[0221] The target compound C was synthesized in the same manner as in Synthesis Example 18, except that intermediates A and B described in Table 2 below were used, respectively.

[0222]

[0223]

[0224] [Synthesis Example 21] Synthesis of Compound 1-4

[0225]

[0226] [Synthesis Example 21-1] Synthesis of Compound 1-4-ii

[0227] 100g (418.3mmol, 1eq) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 61.2g (502.0mmol, 1.2eq) of phenylboronic acid, 419.3g (16.7mmol, 0.04eq) of Pd(PPh3), and 115.6g (836.6mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-4-ii (2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine) (103.3 g, yield 88%).

[0228] Mass: [(M+H) + ] : 280.71

[0229] NMR( 1 H): σ= 7.84(2H, d), 7.70-7.65(2H, m), 7.53-7.49(3H, m), 7.36(1H, t), 7.22(1H, t)

[0230] [Synthesis Example 21-2] Synthesis of Compound 1-4-i

[0231] 103.3g (368.1mmol, 1eq) of 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine, 63.3g (404.9mmol, 1.1eq) of (2-chlorophenyl)boronic acid, 412.8g (11.0mmol, 0.03eq) of Pd(PPh3), and 101.8g (736.2mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-4-i (2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine) (118.2 g, yield 90%).

[0232] Mass: [(M+H) + ] : 356.81

[0233] NMR( 1 H): σ= 7.84(2H, d) 7.70-7.53(8H,m), 7.387.36(3H, m), 7.22(1H, t)

[0234] [Synthesis Example 21-3] Synthesis of Compound 1-4

[0235] 20 g (56.1 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine, 25.9 g (67.3 mmol, 1.2 eq) of 6'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, 0.4 g (1.7 mmol, 0.03 eq) of Pd(OAc), 2.7 g (5.6 mmol, 0.1 eq) of XPhos, and 18.6 g (134.5 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-4 {6'-(2-(4-phenylbenzofuro[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile} (25.3 g, yield 78%).

[0236] Mass: [(M+H) + ] : 579.70

[0237]

[0238] [Synthesis Examples 22 to 24]

[0239] The target compound C was synthesized in the same manner as in Synthesis Example 21, except that intermediates A and B described in Table 4 below were used, respectively.

[0240]

[0241]

[0242] [Synthesis Example 25] Synthesis of Compound 1-7

[0243]

[0244] [Synthesis Example 25-1] Synthesis of Compound 1-7-ii

[0245] 100g (418.3mmol, 1eq) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 61.2g (502.0mmol, 1.2eq) of phenylboronic acid, 19.3g (16.7mmol, 0.04eq) of Pd(PPh3)4, and 115.6g (836.6mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-7-ii (2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine) (104.5 g, yield 89%).

[0246] Mass: [(M+H) + ] : 280.71

[0247] NMR( 1 H): σ= 7.84(2H, d), 7.70-7.65(2H, m), 7.53-7.49(3H, m), 7.36(1H, t), 7.22(1H, t)

[0248] [Synthesis Example 25-2] Synthesis of Compound 1-7-i

[0249] 104.5 g (372.3 mmol, 1 eq) of 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine, 64.0 g (409.5 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 412.9 g (11.2 mmol, 0.03 eq) of Pd(PPh3), and 102.9 g (744.6 mmol, 2 eq) of K2CO3 were added to 1550 ml of THF and 520 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-7-I {2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine} (122.2 g, yield 92%).

[0250] Mass: [(M+H) + ] : 356.81

[0251] NMR( 1 H): σ= 7.84(2H, d) 7.70-7.53(8H,m), 7.387.36(3H, m), 7.22(1H, t)

[0252] [Synthesis Example 25-3] Synthesis of Compound 1-7

[0253] 20 g (56.1 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine, 25.9 g (67.3 mmol, 1.2 eq) of 5'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, 0.4 g (1.7 mmol, 0.03 eq) of Pd(OAc), 2.7 g (5.6 mmol, 0.1 eq) of XPhos, and 18.6 g (134.5 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain compound 1-7, 5'-(2-(4-phenylbenzofuro[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile (24.0 g, yield 74%).

[0254] Mass: [(M+H) + ] : 579.70

[0255]

[0256] [Synthesis Examples 26 to 28]

[0257] The target compound C was synthesized in the same manner as in Synthesis Example 25, except that intermediates A and B described in Table 5 below were used, respectively.

[0258]

[0259]

[0260] [Synthesis Example 29] Synthesis of Compound 1-8

[0261]

[0262] [Synthesis Example 29-1] Synthesis of Compound 1-8-ii

[0263] 100g (418.3mmol, 1eq) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 61.2g (502.0mmol, 1.2eq) of phenylboronic acid, 419.3g (16.7mmol, 0.04eq) of Pd(PPh3), and 115.6g (836.6mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-8-ii (2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine) (104.5 g, yield 89%).

[0264] Mass: [(M+H) + ] : 280.71

[0265] NMR( 1 H): σ= 7.84(2H, d), 7.70-7.65(2H, m), 7.53-7.49(3H, m), 7.36(1H, t), 7.22(1H, t)

[0266] [Synthesis Example 29-2] Synthesis of Compound 1-8-i

[0267] 104.5 g (372.3 mmol, 1 eq) of 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine, 64.0 g (409.5 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 412.9 g (11.2 mmol, 0.03 eq) of Pd(PPh3), and 102.9 g (744.6 mmol, 2 eq) of K2CO3 were added to 1550 ml of THF and 520 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-8-I {2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine} (122.2 g, yield 92%).

[0268] Mass: [(M+H) + ] : 356.81

[0269] NMR( 1 H): σ= 7.84(2H, d) 7.70-7.53(8H,m), 7.387.36(3H, m), 7.22(1H, t)

[0270] [Synthesis Example 29-3] Synthesis of Compound 1-8

[0271] 20 g (56.1 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine, 25.9 g (67.3 mmol, 1.2 eq) of 5'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-3'-carbonitrile, 0.4 g (1.7 mmol, 0.03 eq) of Pd(OAc), 2.7 g (5.6 mmol, 0.1 eq) of XPhos, and 18.6 g (134.5 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-8 {5'-(2-(4-phenylbenzofuro[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-3'-carbonitrile} (22.3 g, yield 69%).

[0272] Mass: [(M+H) + ] : 579.70

[0273]

[0274] [Synthesis Examples 30 and 31]

[0275] The target compound C was synthesized in the same manner as in Synthesis Example 29, except that intermediates A and B described in Table 6 below were used, respectively.

[0276]

[0277]

[0278] [Synthesis Example 32] Synthesis of Compound 1-61

[0279]

[0280] [Synthesis Example 32-1] Synthesis of Compound 1-61-ii

[0281] 100g (418.3mmol, 1eq) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 61.2g (502.0mmol, 1.2eq) of phenylboronic acid, 19.3g (16.7mmol, 0.04eq) of Pd(PPh3)4, and 115.6g (836.6mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-61-ii (2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine) (104.5 g, yield 89%).

[0282] Mass: [(M+H) + ] : 280.71

[0283] NMR( 1 H): σ= 7.84(2H, d), 7.70-7.65(2H, m), 7.53-7.49(3H, m), 7.36(1H, t), 7.22(1H, t)

[0284] [Synthesis Example 32-2] Synthesis of Compound 1-61-i

[0285] 104.5 g (372.3 mmol, 1 eq) of 2-chloro-4-phenylbenzofuro[3,2-d]pyrimidine, 64.0 g (409.5 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 412.9 g (11.2 mmol, 0.03 eq) of Pd(PPh3), and 102.9 g (744.6 mmol, 2 eq) of K2CO3 were added to 1550 ml of THF and 520 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-61-i {2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine} (122.2 g, yield 92%).

[0286] Mass: [(M+H) + ] : 356.81

[0287] NMR( 1 H): σ= 7.84(2H, d) 7.70-7.53(8H,m), 7.387.36(3H, m), 7.22(1H, t)

[0288] [Synthesis Example 32-3] Synthesis of Compound 1-61

[0289] 20 g (56.1 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzofuro[3,2-d]pyrimidine, 31.0 g (67.3 mmol, 1.2 eq) of 4-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl)benzonitrile, 0.4 g (1.7 mmol, 0.03 eq) of Pd(OAc), 2.7 g (5.6 mmol, 0.1 eq) of XPhos, and 18.6 g (134.5 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-61, 4-(2'-(2-(4-phenylbenzofuro[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluoren]-7'-yl)benzonitrile (22.3 g, yield 69%).

[0290] Mass: [(M+H) + ] : 655.80

[0291]

[0292] [Synthesis Examples 33 to 35]

[0293] The target compound d was synthesized in the same manner as in Synthesis Example 32, except that intermediates A, B, and c described in Table 7 below were used, respectively.

[0294]

[0295]

[0296] [Synthesis Example 36] Synthesis of Compound 1-76

[0297]

[0298] [Synthesis Example 36-1] Synthesis of Compound 1-76-ii

[0299] 60 g (251.0 mmol, 1 eq) of 2,4-dichlorobenzofuro[3,2-d]pyrimidine, 39.2 g (251.0 mmol, 1.0 eq) of (2-chlorophenyl)boronic acid, 11.6 g (10.0 mmol, 0.04 eq) of Pd(PPh3), and 69.4 g (502.0 mmol, 2 eq) of K2CO3 were added to 900 ml of THF and 300 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-76-ii {2-chloro-4-(2-chlorophenyl)benzofuro[3,2-d]pyrimidine} (67.2 g, yield 85%).

[0300] Mass: [(M+H) + ] : 315.15

[0301] NMR( 1 H): σ= 7.71-7.65(4H, m), 7.38-7.36(3H, m), 7.22(1H, t)

[0302] [Synthesis Example 36-2] Synthesis of Compound 1-76-i

[0303] 67.2 g (213.3 mmol, 1 eq) of 2-chloro-4-(2-chlorophenyl)benzofuro[3,2-d]pyrimidine, 31.2 g (256.0 mmol, 1.2 eq) of phenylboronic acid, 47.4 g (6.4 mmol, 0.03 eq) of Pd(PPh3), and 59.0 g (426.7 mmol, 2 eq) of K2CO3 were added to 1000 ml of THF and 400 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-76-i {4-(2-chlorophenyl)-2-phenylbenzofuro[3,2-d]pyrimidine} (122.2 g, yield 92%).

[0304] Mass: [(M+H) + ] : 356.81

[0305] NMR( 1 H): σ= 8.35(2H, d), 7.71-7.65(4H, m), 7.50(3H, d), 7.37-7.36(3H, m), 7.22(1H, t)

[0306] [Synthesis Example 36-3] Synthesis of Compound 1-76

[0307] 20 g (56.1 mmol, 1 eq) of 4-(2-chlorophenyl)-2-phenylbenzofuro[3,2-d]pyrimidine, 25.9 g (67.3 mmol, 1.2 eq) of 7'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, 0.4 g (1.7 mmol, 0.03 eq) of Pd(OAc), 2.7 g (5.6 mmol, 0.1 eq) of XPhos, and 18.6 g (134.5 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and heated and stirred under reflux for 8 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 1-76 {7'-(2-(2-phenylbenzofuro[3,2-d]pyrimidin-4-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile} (24.0 g, yield 74%).

[0308] Mass: [(M+H) + ] : 579.70

[0309]

[0310] [Synthesis Examples 37 to 40]

[0311] The target compound D was synthesized in the same manner as in Synthesis Example 36, except that intermediates A, B, and C described in Table 8 below were used, respectively.

[0312]

[0313]

[0314] [Synthesis Example 41] Synthesis of Compound 2-1

[0315]

[0316] [Synthesis Example 41-1] Synthesis of Compound 2-1-ii

[0317] 100g (392.0mmol, 1eq) of 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine, 52.6g (431.2mmol, 1.1eq) of phenylboronic acid, 418.1g (15.7mmol, 0.04eq) of Pd(PPh3), and 108.3g (783.9mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-1-ii {2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine} (100.0 g, yield 86%).

[0318] Mass: [(M+H) + ] : 296.77

[0319] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H, d), 7.84(2H, d), 7.53-7.42(5H,m)

[0320] [Synthesis Example 41-2] Synthesis of Compound 2-1-i

[0321] 100.0 g (337.1 mmol, 1 eq) of 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, 58.0 g (370.8 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 111.7 g (10.1 mmol, 0.03 eq) of Pd(PPh3), and 93.2 g (674.2 mmol, 2 eq) of K2CO3 were added to 1500 ml of THF and 600 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-1-i {2-(2-chlorophenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine} (115.6 g, yield 89%).

[0322] Mass: [(M+H) + ] : 372.87

[0323] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H,d), 7.84(2H, d), 7.71(1H, d), 7.61-7.38(8H, m)

[0324] [Synthesis Example 41-3] Synthesis of Compound 2-1

[0325] 20 g (53.6 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, 24.8 g (64.4 mmol, 1.2 eq) of 7'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, 0.4 g (1.6 mmol, 0.03 eq) of Pd(OAc), 2.6 g (5.4 mmol, 0.1 eq) of XPhos, and 17.8 g (128.7 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-1 {7'-(2-(4-phenylbenzo[4,5]thieno[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile} (23.6 g, yield 74%).

[0326] Mass: [(M+H) + ] : 595.76

[0327]

[0328] [Synthesis Examples 42 to 47]

[0329] The target compound C was synthesized in the same manner as in Synthesis Example 41, except that intermediates A and B described in Table 9 below were used, respectively.

[0330]

[0331]

[0332]

[0333] [Synthesis Example 48] Synthesis of Compound 2-2

[0334]

[0335] [Synthesis Example 48-1] Synthesis of Compound 2-2-ii

[0336] 100g (392.0mmol, 1eq) of 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine, 52.6g (431.2mmol, 1.1eq) of phenylboronic acid, 418.1g (15.7mmol, 0.04eq) of Pd(PPh3), and 108.3g (783.9mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-2-ii {2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine} (100.0 g, yield 86%).

[0337] Mass: [(M+H) + ] : 296.77

[0338] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H, d), 7.84(2H, d), 7.53-7.42(5H,m)

[0339] [Synthesis Example 48-2] Synthesis of Compound 2-2-i

[0340] 100.0 g (337.1 mmol, 1 eq) of 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, 58.0 g (370.8 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 111.7 g (10.1 mmol, 0.03 eq) of Pd(PPh3), and 93.2 g (674.2 mmol, 2 eq) of K2CO3 were added to 1500 ml of THF and 600 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-2-i {2-(2-chlorophenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine} (115.6 g, yield 89%).

[0341] Mass: [(M+H) + ] : 372.87

[0342] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H,d), 7.84(2H, d), 7.71(1H, d), 7.61-7.38(8H, m)

[0343] [Synthesis Example 48-3] Synthesis of Compound 2-2

[0344] 20 g (53.6 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, 24.8 g (64.4 mmol, 1.2 eq) of 2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-6'-carbonitrile, 0.4 g (1.6 mmol, 0.03 eq) of Pd(OAc), 2.6 g (5.4 mmol, 0.1 eq) of XPhos, and 17.8 g (128.7 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-2 {2'-(2-(4-phenylbenzo[4,5]thieno[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-6'-carbonitrile} (23.0 g, yield 72%).

[0345] Mass: [(M+H) + ] : 595.76

[0346]

[0347] [Synthesis Examples 49 to 51]

[0348] The target compound C was synthesized in the same manner as in Synthesis Example 48, except that intermediates A and B described in Table 10 below were used, respectively.

[0349]

[0350]

[0351] [Synthesis Example 52] Synthesis of Compound 2-4

[0352]

[0353] [Synthesis Example 52-1] Synthesis of Compound 2-4-ii

[0354] 100g (392.0mmol, 1eq) of 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine, 52.6g (431.2mmol, 1.1eq) of phenylboronic acid, 18.1g (15.7mmol, 0.04eq) of Pd(PPh3)4, and 108.3g (783.9mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-4-ii {2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine} (100.0 g, yield 86%).

[0355] Mass: [(M+H) + ] : 296.77

[0356] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H, d), 7.84(2H, d), 7.53-7.42(5H,m)

[0357] [Synthesis Example 52-2] Synthesis of Compound 2-4-i

[0358] 100.0 g (337.1 mmol, 1 eq) of 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, 58.0 g (370.8 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 11.7 g (10.1 mmol, 0.03 eq) of Pd(PPh3)4, and 93.2 g (674.2 mmol, 2 eq) of K2CO3 were added to 1500 ml of THF and 600 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-4-I {2-(2-chlorophenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine} (115.6 g, yield 89%).

[0359] Mass: [(M+H) + ] : 372.87

[0360] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H,d), 7.84(2H, d), 7.71(1H, d), 7.61-7.38(8H, m)

[0361] [Synthesis Example 52-3] Synthesis of Compound 2-4

[0362] 20 g (53.6 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, 24.8 g (64.4 mmol, 1.2 eq) of 6'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile, 0.4 g (1.6 mmol, 0.03 eq) of Pd(OAc), 2.6 g (5.4 mmol, 0.1 eq) of XPhos, and 17.8 g (128.7 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-4 {6'-(2-(4-phenylbenzo[4,5]thieno[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile} (22.4 g, yield 70%).

[0363] Mass: [(M+H) + ] : 595.76

[0364]

[0365] [Synthesis Examples 53 to 55]

[0366] The target compound C was synthesized in the same manner as in Synthesis Example 52, except that intermediates A and B described in Table 11 below were used, respectively.

[0367]

[0368]

[0369] [Synthesis Example 56] Synthesis of Compound 2-61

[0370]

[0371] [Synthesis Example 56-1] Synthesis of Compound 2-61-ii

[0372] 100g (392.0mmol, 1eq) of 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine, 52.6g (431.2mmol, 1.1eq) of phenylboronic acid, 18.1g (15.7mmol, 0.04eq) of Pd(PPh3)4, and 108.3g (783.9mmol, 2eq) of K2CO3 were added to 1500ml of THF and 500ml of H2O, and the mixture was heated and stirred under reflux for 6 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-61-ii {2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine} (100.0 g, yield 86%).

[0373] Mass: [(M+H) + ] : 296.77

[0374] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H, d), 7.84(2H, d), 7.53-7.42(5H,m)

[0375] [Synthesis Example 56-2] Synthesis of Compound 2-61-i

[0376] 100.0 g (337.1 mmol, 1 eq) of 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, 58.0 g (370.8 mmol, 1.1 eq) of (2-chlorophenyl)boronic acid, 11.7 g (10.1 mmol, 0.03 eq) of Pd(PPh3)4, and 93.2 g (674.2 mmol, 2 eq) of K2CO3 were added to 1500 ml of THF and 600 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-61-i {2-(2-chlorophenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine} (115.6 g, yield 89%).

[0377] Mass: [(M+H) + ] : 372.87

[0378] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H,d), 7.84(2H, d), 7.71(1H, d), 7.61-7.38(8H, m)

[0379] [Synthesis Example 56-3] Synthesis of Compound 2-61

[0380] 20 g (53.6 mmol, 1 eq) of 2-(2-chlorophenyl)-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine, 29.7 g (64.4 mmol, 1.2 eq) of 4-(2'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluoren]-7'-yl)benzonitrile, 0.4 g (1.6 mmol, 0.03 eq) of Pd(OAc), 2.6 g (5.4 mmol, 0.1 eq) of XPhos, and 17.8 g (128.7 mmol, 2 eq) of K2CO3 were added to 300 ml of toluene, 80 ml of EtOH, and 80 ml of H2O, and heated and stirred under reflux for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-61 {4-(2'-(2-(4-phenylbenzo[4,5]thieno[3,2-d]pyrimidin-2-yl)phenyl)spiro[cyclohexane-1,9'-fluoren]-7'-yl)benzonitrile} (26.7 g, yield 74%).

[0381] Mass: [(M+H) + ] : 671.86

[0382]

[0383] [Synthesis Examples 57 to 59]

[0384] The target compound D was synthesized in the same manner as in Synthesis Example 56, except that intermediates A, B, and C described in Table 12 below were used, respectively.

[0385]

[0386]

[0387] [Synthesis Example 60] Synthesis of Compound 2-77

[0388]

[0389] [Synthesis Example 60-1] Synthesis of Compound 2-77-ii

[0390] 30 g (117.6 mmol, 1 eq) of 2,4-dichlorobenzo[4,5]thieno[3,2-d]pyrimidine, 18.4 g (117.6 mmol, 1.0 eq) of (2-chlorophenyl)boronic acid, 45.4 g (4.7 mmol, 0.04 eq) of Pd(PPh3), and 32.5 g (235.2 mmol, 2 eq) of K2CO3 were added to 450 ml of THF and 150 ml of H2O, and the mixture was heated and stirred under reflux for 5 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-77-ii {2-chloro-4-(2-chlorophenyl)benzo[4,5]thieno[3,2-d]pyrimidine} (31.2 g, yield 80%).

[0391] Mass: [(M+H) + ] : 331.21

[0392] NMR( 1 H): σ= 8.05(1H, d), 7.93(1H, d), 7.71(1H, d), 7.61(1H, d), 7.49-7.38(4H, m)

[0393] [Synthesis Example 60-2] Synthesis of Compound 2-77-i

[0394] 31.2 g (94.1 mmol, 1 eq) of 2-chloro-4-(2-chlorophenyl)benzo[4,5]thieno[3,2-d]pyrimidine, 22.4 g (112.9 mmol, 1.2 eq) of [1,1'-biphenyl]-4-ylboronic acid, 43.3 g (2.8 mmol, 0.03 eq) of Pd(PPh3), and 26.0 g (188.1 mmol, 2 eq) of K2CO3 were added to 450 ml of THF and 150 ml of H2O, and the mixture was heated and stirred under reflux for 4 hours. After completion of the reaction, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-77-i {2-([1,1'-biphenyl]-4-yl)-4-(2-chlorophenyl)benzo[4,5]thieno[3,2-d]pyrimidine} (37.2 g, yield 88%).

[0395] Mass: [(M+H) + ] : 448.97

[0396] NMR( 1 H): σ= 8.05(1H, d), 7.96-7.93(3H, m), 7.75(2H, d), 7.71(1H, d), 7.61(1H, d), 7.49-7.38(7H, m), 7.25(2H, d)

[0397] [Synthesis Example 60-3] Synthesis of Compound 2-77

[0398] 2-([1,1'-biphenyl]-4-yl)-4-(2-chlorophenyl)benzo[4,5]thieno[3,2-d]pyrimidine 20g (44.5mmol, 1eq), 6'-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile 20.6g (53.5mmol, 1.2eq), Pd(OAc) 0.3g (1.3mmol, 0.03eq), XPhos 2.1g (4.5mmol, 0.1eq) and 14.8g (106.9mmol, 2eq) of K2CO3 were added to 300ml of Toluene, 80ml of EtOH, and 80ml of H2O. The mixture was heated and refluxed for 6 hours. After the reaction was completed, the mixture was deactivated with a sufficient amount of water, transferred to a separatory funnel, and MC was added. The organic layer was separated and extracted. The extracted organic layer was concentrated, then adsorbed onto silica gel and purified by column chromatography to obtain the target compound 2-77 {6'-(2-(2-([1,1'-biphenyl]-4-yl)benzo[4,5]thieno[3,2-d]pyrimidin-4-yl)phenyl)spiro[cyclohexane-1,9'-fluorene]-2'-carbonitrile} (22.7 g, yield 76%).

[0399] Mass: [(M+H) + ] : 671.86

[0400]

[0401] [Synthesis Examples 61 to 63]

[0402] The target compound D was synthesized in the same manner as in Synthesis Example 60, except that intermediates A, B, and C described in Table 13 below were used, respectively.

[0403]

[0404]

[0405] [Example 1] Fabrication of a blue organic electroluminescent device

[0406] After the compound 1-1 synthesized in the above synthesis example was purified by sublimation to high purity using a commonly known method, a blue organic electroluminescent device was manufactured according to the following process.

[0407] First, a glass substrate coated with a 1200 Å thick ITO (Indium Tin Oxide) film was ultrasonically cleaned in distilled water. After the distilled water cleaning was completed, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and then transferred to a UV OZONE cleaner (Power Sonic 405, Hwasin Tech). The substrate was then cleaned for 5 minutes using UV and transferred to a vacuum deposition machine.

[0408] On the ITO transparent electrode prepared as above, an organic electroluminescent device was manufactured by stacking 98 wt% HI + 2 wt% HAT-CN6 (10 nm) / HI (140 nm) / EB (5 nm) / 98 wt% BH + 2 wt% BD (20 nm) / compound 1-1 + Liq (1:1 weight ratio) (30 nm) / LiF (1 nm) / Al (100 nm) in that order. The structures of the compounds HI, HAT-CN6, EB, BH, BD, and Liq used here are as follows, respectively.

[0409]

[0410]

[0411] [Examples 2 to 63] Preparation of blue organic electroluminescent devices

[0412] A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except that each compound described in Table 14 was used instead of Compound 1-1 used as an electron transport layer material in Example 1.

[0413]

[0414] [Comparative Examples 1 to 8] Manufacturing of blue organic electroluminescent devices

[0415] A blue organic electroluminescent device was manufactured in the same manner as in Example 1, except that Alq3 and compounds E-1 to E-7 were used instead of compound 1-1 used as an electron transport layer material in Example 1. At this time, the structures of Alq3 and compounds E-1 to E-7 used are as follows, respectively.

[0416]

[0417]

[0418] [Evaluation Example 1]

[0419] For the organic electroluminescent devices manufactured in Examples 1 to 63 and Comparative Examples 1 to 8, the driving voltage, emission wavelength, and current efficiency at a current density of 10 mA / cm2 were measured, and the results are shown in Table 14 below.

[0420] Sample Electron Transport Layer Material Driving Voltage (V) Luminescence Peak (nm) Current Efficiency (cd / A) Example 1 Compound 1-1 3.545 27.9 Example 2 Compound 1-2 3.545 37.8 Example 3 Compound 1-3 3.545 47.7 Example 4 Compound 1-4 3.445 27.8 Example 5 Compound 1-7 3.545 47.8 Example 6 Compound 1-8 3.645 77.7 Example 7 Compound 1-9 3.445 57.8 Example 8 Compound 1-10 3.545 67.8 Example 9 Compound 1-12 3.545 57.7 Example 10 Compound 1-13 3.545 27.9 Example 11 Compound 1-143.44507.8 Example 12 Compound 1-163.44517.7 Example 13 Compound 1-173.44547.8 Example 14 Compound 1-183.54538.0 Example 15 Compound 1-243.44548.0 Example 16 Compound 1-253.44558.1 Example 17 Compound 1-263.34517.7 Example 18 Compound 1-303.44537.9 Example 19 Compound 1-373.34507.6 Example 20 Compound 1-353.44557.8 Example 21 Compound 1-433.44537.8 Example 22 Compound 1-453.54558.0 Example 23 Compound 1-463.54527.9 Example 24 Compound 1-513.44547.9 Example 25 Compound 1-523.44517.8 Example 26 Compound 1-613.34507.6 Example 27 Compound 1-623.44547.9 Example 28 Compound 1-713.34517.9 Example 29 Compound 1-733.64508.0 Example 30 Compound 1-763.34507.7 Example 31 Compound 1-793.44537.8 Example 32 Compound 1-803.44567.9 Example 33 Compound 1-8 13.44557.8 Example 34 Compound 1-9 63.54578.0 Example 35 Compound 1-10 63.64588.1 Example 36 Compound 1-10 73.54578.0 Example 37 Compound 1-11 13.54567.8 Example 38 Compound 1-12 13.54568.0 Example 39 Compound 1-12 73.54547.8 Example 40 Compound 1-12 93.44537.7 Example 41 Compound 2-13.54527.8 Example 42 Compound 2-2 3.54557.9 Example 43 Compound 2-4 3.44557.8 Example 44 Compound 2-93.54568.0 Example 45 Compound 2-133.44557.8 Example 46 Compound 2-163.34547.8 Example 47 Compound 2-193.44558.0 Example 48 Compound 2-253.44578.0 Example 49 Compound 2-343.34517.8 Example 50 Compound 2-513.44558.0 Example 51 Compound 2-613.34517.8 Example 52 Compound 2-623.54547.9 Example 53 Compound 2-703.44588.0 Example 54 Compound 2-713.34598.0 Example 55 Compound 2-773.44547.9 Example 56 Compound 2-853.54568.1 Example 57 Compound 2-913.44557.9 Example 58 Compound 2-963.34507.8 Example 59 Compound 2-1063.64578.1 Example 60 Compound 2-1073.54598.0 Example 61 Compound 2-1213.54567.9 Example 62 Compound 2-1273.54578.0 Example 63 Compound 2-1443.34557.8 Comparative Example 1 Alq34.64575.6 Comparative Example 2 E-14.34616.3 Comparative Example 3E-24.14666.4Comparative Example 4E-34.84534.7Comparative Example 5E-43.94526.0Comparative Example 6E-54.04556.5Comparative Example 7E-63.74576.4Comparative Example 8E-74.94665.3.

[0421] From the above Table 14, it was confirmed that the organic light-emitting devices manufactured in Examples 1 to 63 were superior in driving voltage, emission peak, and current efficiency compared to the organic light-emitting devices manufactured in Comparative Examples 1 to 8. In particular, the compound of the present invention contains a fused heteroaromatic ring moiety in which a monocyclic nitrogen-containing heteroaromatic ring (e.g., a pyrimidine ring, etc.) and a benzoic ring (e.g., a benzofuran ring, etc.) are fused, and it was confirmed that the organic light-emitting devices of Examples 1 to 63 using such a compound of the present invention as an electron transport layer material were superior in driving voltage and current efficiency compared to the organic light-emitting devices of Comparative Examples 2 to 3 using a compound containing a monocyclic azine group (e.g., a pyridine group) or a quinoline group (e.g., compounds E-1 and E-2) as an electron transport layer material. In particular, it was confirmed that the devices of Examples 1 to 63 had a greater improvement in driving voltage than the devices of Comparative Examples 2 to 3. This is because the single-ring nitrogen-containing heteroaromatic ring (e.g., pyrimidine ring, etc.) in the condensed heteroaromatic ring moiety of the compound has a wide conjugation area, so it was found that more electrons are distributed in the condensed heteroaromatic ring moiety, resulting in excellent initial driving voltage and total charge transport capacity.

[0422] In addition, the condensed heteroaromatic ring moiety of the compound according to the present invention can perform the role of EWG because it has more electrons than a general dibenzofuran group, and thus the electron injection and transport properties of the compound can be improved. Accordingly, it was found that the devices of Examples 1 to 63 using the compound of the present invention as an electron transport layer material were effective in improving not only the driving voltage but also the current efficiency, compared to Comparative Example 4 using a compound containing a dibenzofuran group (e.g., ET-3) as an electron transport layer material.

[0423] In addition, since the compound according to the present invention has a cyano group substituted on one side of the spiro[cyclohexane-1,9'-fluorene] moiety, the interaction with the adjacent cathode is improved, so that the electron injection characteristics as well as the initial charge generation can be improved, and thus a larger amount of electrons can be obtained from the cathode and transported to the light-emitting layer. Therefore, the devices of Examples 1 to 63 applying the compound of the present invention were able to improve the luminous efficiency while improving the initial driving voltage, compared to Comparative Example 5 applying a compound having a condensed moiety in which the cyano group is unsubstituted (e.g., ET-4). In addition, since the compound of the present invention has a larger dipole moment due to the substituted cyano group, the stacking between the electrode and the organic material is increased, so that defects within the device can be minimized.

[0424] In addition, the compound according to the present invention has the effect of separating the LUMO - HOMO orbitals by appropriately splitting the spiro [cyclohexane-1,9'-fluorene] moiety, which is an electron donating group (EDG) with a large electron donating property, and the condensed heteroaromatic ring moiety, which is an electron withdrawing group (EWG) with a large electron absorbing property, by connecting the fused heteroaromatic ring moiety and the spiro [cyclohexane-1,9'-fluorene] moiety with an arylene group, which is a linker, and thereby improving the bandgap and enabling the device to have an appropriate LUMO energy. Therefore, it was found that the devices of Examples 1 to 63 using the compound of the present invention had lower operating voltages and higher current efficiency compared to the device of Comparative Example 6 using a compound (DP: ET-5) not including a linker.

[0425]

[0426] [Example 64] Fabrication of a blue organic electroluminescent device

[0427] Compound 1-1 synthesized in the above Synthesis Example 1 was purified by high-purity sublimation using a commonly known method, and then a blue organic electroluminescent device was manufactured according to the following process.

[0428] First, a glass substrate coated with a 1200 Å thick ITO (Indium Tin Oxide) film was ultrasonically cleaned in distilled water. After the distilled water cleaning was completed, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and then transferred to a UV OZONE cleaner (Power Sonic 405, Hwasin Tech). The substrate was then cleaned for 5 minutes using UV and transferred to a vacuum deposition machine.

[0429] On the ITO transparent electrode prepared as above, an organic electroluminescent device was manufactured by stacking 98 wt% HI + 2 wt% HAT-CN6 (10 nm) / HI (140 nm) / EB (5 nm) / 98 wt% BH + 2 wt% BD (20 nm) / compound 1-1 (5 nm) / ET + Liq (1:1 weight ratio) (30 nm) / LiF (1 nm) / Al (100 nm) in that order. At this time, the structures of HI, HAT-CN6, EB, BH, BD, ET, and Liq used are as follows, respectively.

[0430]

[0431]

[0432] [Examples 65 to 126] Preparation of blue organic electroluminescent devices

[0433] A blue organic electroluminescent device was manufactured in the same manner as in Example 65, except that each of the compounds described in Table 15 below was used instead of Compound 1-1 used as an electron transport auxiliary layer material in Example 64.

[0434]

[0435] [Comparative Example 9] Fabrication of a blue organic electroluminescent device

[0436] A blue organic electroluminescent device was manufactured in the same manner as in Example 65, except that compound 1-1, which was used as an electron transport auxiliary layer material in Example 64, was not used.

[0437]

[0438] [Comparative Examples 10 to 16] Manufacturing of blue organic electroluminescent devices

[0439] A blue organic electroluminescent device was manufactured in the same manner as in Example 64, except that Compounds E-1 to E-7 were used instead of Compound 1-1, which was used as an electron transport auxiliary layer material in Example 64. At this time, the structures of Compounds E-1 to E-7 used are as follows, respectively.

[0440]

[0441]

[0442] [Evaluation Example 2]

[0443] For the organic electroluminescent devices manufactured in Examples 64 to 126 and Comparative Examples 10 to 16, the driving voltage, emission wavelength, and current efficiency at a current density of 10 mA / cm2 were measured, and the results are shown in Table 15 below.

[0444] Sample Electron Transport Auxiliary Layer Material Driving Voltage (V) Luminescence Peak (nm) Current Efficiency (cd / A) Example 64 Compound 1-1 3.445 18.0 Example 65 Compound 1-2 3.345 17.9 Example 66 Compound 1-3 3.445 37.9 Example 67 Compound 1-4 3.445 37.8 Example 68 Compound 1-7 3.445 48.0 Example 69 Compound 1-8 3.545 57.8 Example 70 Compound 1-9 3.345 67.9 Example 71 Compound 1-10 3.345 57.8 Example 72 Compound 1-12 3.445 47.8 Example 73 Compound 1-133.34557.8 Example 74 Compound 1-143.24548.0 Example 75 Compound 1-163.24537.9 Example 76 Compound 1-173.34527.9 Example 77 Compound 1-183.44548.3 Example 78 Compound 1-243.34548.1 Example 79 Compound 1-253.24538.2 Example 80 Compound 1-263.24527.8 Example 81 Compound 1-303.34518.0 Example 82 Compound 1-373.44537.7 Example 83 Compound 1-353.34547.9 Example 84 Compound 1-433.44537.8 Example 85 Compound 1-453.44528.2 Example 86 Compound 1-463.44538.0 Example 87 Compound 1-513.34547.9 Example 88 Compound 1-523.44537.9 Example 89 Compound 1-613.44527.7 Example 90 Compound 1-623.34528.1 Example 91 Compound 1-713.44548.1 Example 92 Compound 1-733.54518.2 Example 93 Compound 1-763.24537.8 Example 94 Compound 1-793.34547.9 Example 95 Compound 1-803.24537.9 Example 96 Compound 1-813.34538.0 Example 97 Compound 1-963.44538.2 Example 98 Compound 1-1063.54528.3 Example 99 Compound 1-1073.54518.1 Example 100 Compound 1-1113.44537.8 Example 101 Compound 1-1213.44548.1 Example 102 Compound 1-1273.54547.7 Example 103 Compound 1-1293.44537.8 Example 104 Compound 2-13.34537.9 Example 105 Compound 2-23.44527.8 Example 106 Compound 2-43.44518.0 Example 107 Compound 2-9 3.44538.1 Example 108 Compound 2-13 3.34537.9 Example 109 Compound 2-16 3.34547.7 Example 110 Compound 2-19 3.44558.1 Example 111 Compound 2-25 3.34528.2 Example 112 Compound 2-34 3.24517.9 Example 113 Compound 2-5 13.34567.9 Example 114 Compound 2-6 13.34547.8 Example 115 Compound 2-62 3.44538.2 Example 116 Compound 2-70 3.34558.1 Example 117 Compound 2-713.44578.1 Example 118 Compound 2-773.44538.0 Example 119 Compound 2-853.44538.0 Example 120 Compound 2-913.34548.0 Example 121 Compound 2-963.34527.9 Example 122 Compound 2-1063.54568.2 Example 123 Compound 2-1073.44578.0 Example 124 Compound 2-1213.44547.7 Example 125 Compound 2-1273.34567.9 Example 126 Compound 2-1443.34547.9 Comparative Example 9-4.94575.3Comparative example 10E-14.24606.5Comparative example 11E-24.14636.6Comparative example 12E-34.74574.5Comparative example 13E-44.04556.4Comparative example 14E-54.14546.3Comparative example 15E-64.24616.3Comparative example 16E-75.34685.2.

[0445] From Table 15 above, it was confirmed that the organic light-emitting devices manufactured in Examples 64 to 126 had superior driving voltage, emission peak, and current efficiency compared to the organic light-emitting devices manufactured in Comparative Examples 9 to 16. In addition, it was found that when the compound according to the present invention was applied to the electron transport layer, the driving voltage of the device was improved, whereas when the compound according to the present invention was applied to the electron transport auxiliary layer, the efficiency of the device was greatly improved.

[0446] In particular, it was found that the devices of Examples 64 to 126, in which the compound according to the present invention was applied to the electron transport auxiliary layer, showed improvements in both the driving voltage and current efficiency compared to the device of Comparative Example 7, which did not include the electron transport auxiliary layer. Accordingly, it was found that the compound of the present invention helps improve the current efficiency of the device by confining excitons within the light-emitting layer. In addition, since the compound of the present invention has excellent electron transport properties and thus excellent electron transfer ability from the electron transport layer to the light-emitting layer, the driving voltage of the device could also be improved.

[0447] In addition, the devices of Examples 64 to 126, in which the compounds according to the present invention were applied to the electron transport auxiliary layer, exhibited superior operating voltage and current efficiencies compared to the devices of Comparative Examples 9 to 16, in which compounds E-1 to E-7 were used, respectively. Accordingly, it was found that the compounds according to the present invention had superior electron transport capabilities compared to compounds E-1 to E-7.

Claims

1. A compound represented by the following chemical formula 1: [Chemical Formula 1] (In the above chemical formula 1, X 1 Inland X 4 are identical or different from each other, and each independently represents N or C(Ar 1 ) and only X 1 Inland X 4 At least two of them are N; Y 1 Silver O, S, Se, C(Ar 2 )(Ar 3 ) and N(Ar 4 ) is selected from the group consisting of, a is 1 or 2, b is an integer from 0 to 4, R 1 , R 2 , and Ar 1 Inland Ar 4 are identical or different from each other, and each independently represents hydrogen, deuterium (D), a halogen group, a cyano group, a nitro group, an amino group, a hydroxyl group, C 1 ~C 40 Alkyl group of C 2 ~C 40 Alkenyl group of C 2 ~C 40 Alkynyl group of C 3 ~C 40 A cycloalkyl group of , a heterocycloalkyl group having 3 to 40 nuclear atoms, C 6 ~C 60 Aryl group of, heteroaryl group having 5 to 60 nuclear atoms, C 1 ~C 40 Alkyloxy group of C 6 ~C 60 Aryloxy group of C 1 ~C 40 Alkylsilyl group of C 6 ~C 60 Arylsilyl group of C 1 ~C 40 Alkylboron group of C 6 ~C 60 Aryl boron group, C 6 ~C 60 Arylphosphine group of C 6 ~C 60 Arylphosphine oxide group and C 6 ~C 60 is selected from the group consisting of arylamine groups; n is an integer from 1 to 4, L 1 Silver C 6 ~C 18 is an arylene group, Above R 1 , R 2 , and Ar 1 Inland Ar 4 An alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group, an arylboron group, an arylphosphine group, an arylphosphine oxide group and an arylamine group, and the L 1 The arylene groups are each independently selected from deuterium (D), halogen, cyano group, nitro group, amino group, hydroxy group, C 1 ~C 40 Alkyl group of C 2 ~C 40 Alkenyl group of C 2 ~C 40 Alkynyl group of C 3 ~C 40 A cycloalkyl group of , a heterocycloalkyl group having 3 to 40 nuclear atoms, C 6 ~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C 1 ~C 40 Alkyloxy group of C 6 ~C 60 Aryloxy group of C 1 ~C 40 Alkylsilyl group of C 6 ~C 60 Arylsilyl group of C 1 ~C 40 Alkylboron group of C 6 ~C 60 Aryl boron group, C 6 ~C 60 Arylphosphine group of C 6 ~C 60 Arylphosphine oxide group and C 6 ~C 60 (Substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, and when there are multiple substituents, they are the same or different from each other).

2. In paragraph 1, Above A compound selected from the group consisting of the following moieties Mo1-1 to Mo1-34: (In the above moieties Mo1-1 to Mo1-34, Y 1 , b, R 1 and R 2 are as defined in Article 1, respectively, b1 is an integer from 0 to 3).

3. In paragraph 1, Above X 1 Inland X 4 Two of them are N compounds.

4. In paragraph 1, Above L 1 A compound selected from the group consisting of the following linker groups L1-1 to L1-11: (In the above linker groups L1-1 to L1-11, c is an integer from 0 to 4, d is an integer from 0 to 6, e is an integer from 0 to 8, f is an integer from 0 to 7, g is an integer from 0 to 3, h is an integer from 0 to 5, i is an integer from 0 to 10, Multiple R's are identical or different from each other, R is deuterium (D), halogen, cyano group, nitro group, amino group, hydroxy group, C 1 ~C 40 Alkyl group of C 2 ~C 40 Alkenyl group of C 2 ~C 40 Alkynyl group of C 3 ~C 40 A cycloalkyl group of , a heterocycloalkyl group having 3 to 40 nuclear atoms, C 6 ~C 60 Aryl group of , heteroaryl group having 5 to 60 nuclear atoms, C 1 ~C 40 Alkyloxy group of C 6 ~C 60 Aryloxy group of C 1 ~C 40 Alkylsilyl group of C 6 ~C 60 Arylsilyl group of C 1 ~C 40 Alkylboron group of C 6 ~C 60 Aryl boron group, C 6 ~C 60 Arylphosphine group of C 6 ~C 60 Arylphosphine oxide group and C 6 ~C 60 (selected from the group consisting of arylamine groups).

5. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 2 to 9: [Chemical formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical formula 6] [Chemical formula 7] [Chemical formula 8] [Chemical formula 9] (In the above chemical formulas 2 to 9, X 1 Inland X 4 , Y 1 , a, b, R 1 , R 2 , n and L 1 are as defined in Article 1, respectively, b 1 is an integer from 0 to 3).

6. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by the following chemical formula 10 or 11: [Chemical Formula 10] [Chemical Formula 11] (In the above chemical formulas 10 and 11, X 1 Inland X 4 , Y 1 , a, b, R 1 , R 2 are as defined in Article 1, respectively, b 1 is an integer from 0 to 3).

7. In paragraph 1, The compound represented by the above chemical formula 1 is a compound represented by any one of the following chemical formulas 12 to 15: [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] [Chemical Formula 15] (In the above chemical formulas 12 to 15, Y 1 , b, R 2 , n are as defined in Article 1, respectively. Multiple R's 1 are identical or different from each other, R 1 Silver C 6 ~C 60 is selected from the group consisting of an aryl group and a heteroaryl group having 5 to 60 nuclear atoms, Above R 1 The aryl group and heteroaryl group are each independently selected from deuterium (D), halogen, cyano group, nitro group, amino group, hydroxy group, C 1 ~C 40 Alkyl group of C 6 ~C 60 An aryl group of , a heteroaryl group having 5 to 60 nuclear atoms, and C 6 ~C 60 is substituted or unsubstituted with one or more substituents selected from the group consisting of arylamine groups, and when there are multiple substituents, they are the same or different from each other, b1 is an integer from 0 to 3).

8. In paragraph 1, The compound represented by the above chemical formula 1 is a compound selected from the group consisting of the following compounds: .

9. Anode; cathode; comprising at least one organic layer interposed between the anode and cathode, An organic electroluminescent device, wherein at least one of the organic layers of the above one or more layers comprises a compound according to any one of claims 1 to 8.

10. In paragraph 9, An organic electroluminescent device, wherein the organic layer containing the above compound is an electron transport layer or an electron transport auxiliary layer.

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