TW200806626A - Amine compound containing carbazol and uses thereof - Google Patents

Abstract

An objective of the present invention is to provide an amine compound containing carbazol having a high Tg and easy to form a stable thin film because of its difficultly-crystallized molecular. When the amine compound of the present invention is used as an organic EL element material, excellent properties such as low voltage driving, long service life can be obtained. The present invention relates to the amine compound containing carbazol represented by the following formula [1]. Formula [1] (wherein Ar1 represents a carbazolyl group represented by the following formula [2]; Ar2 to Ar4 independently represent a monovalent aromatic hydrocarbon group, a monovalent heterocycle group; A represents an arylene group having a carbon number of 10 to 30) Formula [2] (wherein Ar5 represents a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocycle group; R1 to R7 independently represent a hydrogen atom, a halogen atom or a monovalent organic residue)

Description

200806626 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a novel amine compound containing a material, which is more like + =1!, which is an organic electroluminescent element (hereinafter referred to as "the ancient" , because the crystallinity of the molecule is low, and the glass transition temperature (Tg) contains the amine compound of (4). [Long-term, two-safety] [Prior Art] In the case of a card-salting organism, it is applied to various functional materials, Discussion on the surface of electronic materials. The hat rack has a hole transporting property and a two-dimensional structure, and has a discussion on the use of the characteristics of the (four) frame to apply to the charge transporting material of the photoreceptor or the material of the organic EL element. The compound is widely used as a material for an organic EL device (see Non-Patent Document 1, and Z, the organic EL device is driven or protected). f, will produce light color ^% horse plastic hair ^ rate reduction, drive voltage rise, luminescence life is shortened, etc. ^ In order to prevent these adverse effects, it is necessary to improve the material break the private temperature (Tg) Although the Tg is more heat-resistant, such as PVK or coffee, although it has a structure with high symmetry, when the film is formed by direct space =, spin coating, or the like, the film property is lowered: It is easy, and the life of the crystal and the element are extremely reduced. ° In this case, a diamine compound in which the third group of N-ethylcarbazole is substituted is disclosed (see Non-Patent Documents 3 and 4, Patent). 319365 6 200806626 献 l) These diamine compounds have a work The hole injection material, the appropriate IP' of the hole input material, and the non-crystallinity due to the asymmetry of the σ-嗤 ring, have a high degree of film stability, but on the other hand, the Tg is not high enough to be heat-resistant. Poor EL element does not provide sufficient life characteristics. Non-Patent Document 1: Applied Physics Letters, 2001, vol. 78, p. 278 pp. Non-Patent Document 2 ·· Journal 〇f the American Chemistry

Society, 2001, Vol. 123, p. 4304

Non-Patent Document 3 ································································· SUMMARY OF THE INVENTION (Problems to be Solved by the Invention) An object of the present invention is to provide a bismuth-containing compound having a high Tg and having a high Tg, which is difficult to crystallize, and is used for an organic EL device. In the case of a material, it is a low-voltage, and it is a low-voltage drive. When it is a member, it is less harmful to an organic compound, and it can be easily solved (the method for solving the problem). The present inventors conducted intensive studies to solve the above problems, 319365 7 200806626 'The result is the invention. That is, the present invention relates to an oxazole-containing amine compound represented by the following general formula [1]: General formula [1] na J2.

Wherein 'Ar represents a carbazolyl group represented by the general formula [2]; and Ar2 to Ar4 each independently represent a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, or a carbon number which may have a substituent a monovalent heterocyclic group of 2 to 18 (except for the case of the following general formula [2]); a represents a carbon number which may have a substituent of 1 〇 to an extended aryl group) [2]

(wherein, Ar5 represents a monovalent aromatic diyl group having 6 to 18 carbon atoms which may have a substituent, or a monovalent aromatic algebra having a carbon number of 2 to 18 which may have a substituent: a base, and R1 to R7 respectively Independently represents a hydrogen atom, a dentate atom or a monovalent organic residue). Further, the present invention is characterized by the general formula [3] characterized by the fact that A is represented by the following general formula [3]: Benzene 319365 8 200806626 (biphenylene).

The bond, the remaining ones are independently a hydrogen atom, a argon atom or an adjacent organic residue may form a ring with each other. Further, the present invention relates to the use of A as the aforementioned carbazole-containing amine compound: General formula [4] One is a combination of a monovalent organic residue, and the following formula [4] is characterized.

(wherein R3G to R37 represent an argon atom, R30 and R31, R32 and R33, and β34 and R35 may be bonded to each other to form a ring). a halogen atom or a monovalent organic residue; or R36 and R37, a substituent, and the present invention relates to the above-described taste-containing amine compound characterized by Ar5 being represented by the following general formula [5]. General formula [5] 319365 9 200806626

(wherein R38 represents a hydrogen atom, a dentate atom, a cyclinyl group, a fluorene group, a di-calyx anthracene group having a carbon number of 6 to 12 which may have a substituent, and a carbon number of 2 to 2 which may have a substituent 5-valent heterocyclic group). The present invention relates to a material for an organic electroluminescence device comprising the above-mentioned amine containing carbazole. σ ′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′′ The material for the organic electroluminescence device is made of the above. Further, the present invention relates to an organic electroluminescence device which is characterized in that the hole injection layer and/or hole transport are carried out in an organic electroluminescence device having a hole injection layer and/or a hole transport layer. The layer is made of a material containing the above-mentioned organic electroluminescence element. In order to explain the present invention in more detail, the present invention is as described in the following (1) to (12). (1) An amine compound containing carbazole represented by the following formula [丨] · Formula [1]

Ar1, Ar2 Ν

Ar4 Ν·

Ar3 ίο 319365 200806626 (wherein Ar1 represents an oxazolyl group represented by the following formula [2]. [2]

(wherein 'Ar5 represents a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, 1 or a monovalent aromatic heterocyclic ring having 2 to 10 carbon atoms which may have a substituent: R to R are independently Represents a hydrogen atom, a halogen atom or a monovalent organic residue); Ar2 to Ar4 each independently represent a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent, and a carbon number 2 to oxime which may have a substituent The heterocyclic group (except for the case of the oxime group represented by the above formula [2]), and the table A may not have a substituent having a carbon number of 丨〇 to 3 伸 of an extended aryl group). (^) an amine compound containing carbazole as described in (1), wherein

Ar is a phenyl group which may have a substituent represented by the following general formula [5].

(wherein alkyl, 'R38 represents a hydrogen atom, a carbon number atom in which a halogen may have a substituent, a cyano group, a 6 to 12 carbon monovalent aromatic hydrocarbon group having 1 to 3 carbon atoms, or 319365 11 200806626 may have a substituent a monovalent heterocyclic group having 2 to 5 carbon atoms). (3) The amine compound containing carbazole according to (2), wherein R in the formula [5] is a halogen atom, a halogen atom, a cyano group, an alkyl group having a carbon number of 3, a phenyl group, or 4-bite base. (4) The carbazole-containing amine compound according to any one of (1) to (3), wherein Ri to R? in the formula [2] is a ruthenium atom. (5) The oxazole-containing amine compound according to any one of (1) to (4), wherein the A group in the general formula [1] may be an alkyl group having a carbon number of 5 or a halogen atom. Substituted 4, 4, -biphenyl, 3,3'-biphenyl substituted by a C 1 to 5 alkyl group or a halogen atom, an alkyl group having a carbon number of 5 or a halogen a 2, 2'-terphenyl substituted by an atom, a 1,4-naphthyl group which may be substituted with an alkyl group having a carbon number of 5 or a halogen atom, or an alkyl group having a carbon number of i to 5 Or an i,5-naphthyl group substituted by a halogen atom. (6) The carbazole-containing amine compound according to any one of (1) to (4), wherein the A in the general formula [1] is a biphenyl group represented by the following formula [3]: Formula [3]

The remaining knives are independently hydrogen atoms, halogen atoms or adjacent organic residues which form a ring with each other). The ash & base (7) is an amine compound containing the octagonal as in the above (8), and 319365 12 200806626 A in the formula (1) is a 4,4,-extended biphenyl formula represented by the following formula [4] [ 4]

R32 R(10) 'R37 C where R30 δ Ρ37 ^ - >tr κ represents an oxygen atom, a halogen atom or a monovalent organic residue; R and R, R32 and R33, R34 and R35, or R36 and R37, a substituent They can be combined with each other to form a ring). (8) The carbazole-containing amine compound according to any one of (1) to (6), wherein the A group 4, 4, a biphenyl group, 2, 2, one in the general formula [1] Dimercapto- 4, 4, a biphenylene group, 3, 3, a biphenyl group, or a 2, 2, a biphenyl group. (8) An amine compound containing a decyl group as defined in any one of (4) to (8), wherein the indole 4, 4, - is extended to a biphenyl group in the formula [1]. (^^有-electromechanical hair-emitting material' is made of the amine compound containing the carbazole of the above (1) 壬- item. The electroluminescent element 'is formed between the pair of electrodes to form a luminescence" An organic electroluminescent element made of an organic layer of a plurality of layers of a first layer, wherein at least a layer of the organic layer is made of a material for an organic electroluminescence device. It is an organic electroluminescence device having an electric/hole transport layer, and the ^"second and/or hole transport layer is made of a material for containing, and implanting a hole into the layer. "(1)) Organic electroluminescent element 319365 13 200806626 • (Effect of the invention) The organic EL element obtained by using the saliva-containing amine compound of the present invention has a low driving voltage and long life due to the film of the film. Hanging, TV and other flat panel displays or flat illuminators, and can be applied to light sources such as ^, hanging watch machines, liquid crystal displays or metering::: printed logo lights, etc. You are not board, [implementation]: Second, the present invention will be described in detail. An amine compound containing a carbazole. A fly aryl group having a carbon number of 10 to 30 having a substituent represented by the general formula [1], and not having a carbon number of 1 G. The exoaryl group to 3{) may, for example, be a polycyclic or condensed cyclic aromatic group of up to 30, a stretched biphenyl group, an extension of mm w such as a succinyl group, a succinyl group, etc. nthrylene), Examples of the substituent of the stretching group 1 to S 'diaryl group include a linear or branched burning group having a carbon number of 1 to 30 (the enthalpy is enthalpy;直 is better) of the direct-bonded or branched filaments; i-atomic atoms; by! 5 (1 to 3 are preferred) phenolic atoms replaced by 1 to 1 碳 (and even better) a linear or branched base; a radical, etc., but not only (for examples of preferred substituents in the aryl group, examples of: substituents: ethyl, ethyl, An oxy group, an ethoxy group, a trichloromethyl group, a trifluoromethyl group, a gas atom, a fluorine atom, a nitro group, etc. Further, in the case of a substituent of an extended aryl group, 319365 14 _626 • may also be an aryl group, a phase Neighboring atoms are combined with each other, and $ atoms The group consisting of a condensed 5-membered heterocyclic ring or a condensed 6-membered heterocyclic 5-shelled ring, a condensed 6-membered ring, an alkane ring formed by bonding between adjacent groups, a cyclopentene ring, etc. The cyclopentyl adjacent groups are combined with each other to form a 6-shell ring, which can be listed as γ Μ, cyclohexyl _, benzene ring, etc. 1 as a mixture of adjacent groups and oxygen The ring, each pyridine ring, ^t " chen, may be exemplified by a diphene ring, an imidazole ring, a work soil, a furan ring, a pyrrole ring, a thiophene, a pyrazole ring, a carbazole ring, a thiazole ring, and the like. The 6-membered heterocyclic ring formed by the combination of the pyridine ring and the ί ring may be exemplified by a ratio of a f coat, a mouth ring, a tart ring, and a pyranone ring. Zhongfeiji: Γ 'It is better to stretch naphthyl, extend biphenyl, lyon, and pass two m'. It is better to extend the biphenyl represented by the general formula [3]. 4] 4, 4, _ stretched biphenyl is particularly good. The preferred group A in the general formula (1) of 1 U may, for example, be 4,4,-diphenyl, keyl, and human 1 which may be substituted by a carbaryl or a halo atom. a 2, 2, -extension, carbon number substituted by a 3, 3, - a biphenyl group which may be substituted with an alkyl group or a halogen atom, or an alkyl group having 1 to 5 divalent groups or a halogen atom a group of 1 to 5 alkyl or a dentate atom substituted with a fluorene, a 4i i 5 group or a fluorene may be substituted with an alkyl group having 1 to 5 carbon atoms or a halogen atom, and a preferred group. A is 4, 4, -biphenyl, 2, 2,-dixia ^ 4' 4 - biphenyl, 3, 3' ~ biphenyl, 2, 2, - exophenyl, ' ~ Stretching Cai, 1,5-stretching naphthyl and so on. A particularly desirable base a is 4, 4, a stretch of 15 319365 200806626 A biphenyl. In the general formula [1], Ar2 to Ar4 represent a monovalent aromatic hydrocarbon group having 6 7 ^ carbon atoms which may have a substituent, and a heterocyclic group having 2 to 18 carbon atoms which may have a substituent (only, general formula [ Except in the case of 2]). In this case, the monovalent aromatic furnace f having 6 to 18 carbon atoms which may have a substituent may, for example, be a phenyl group, a naphthyl group, a biphenyl group, a thiol group, a phenanthryl group, a g group, a group, or a 3- Methylphenyl, 3-methoxyphenyl, 3-fluorophenyl, 3-tris-trimethyl-yl, 3-trifluoromethylphenyl, 3-Schishylphenyl, and the like. Among them, phenyl, naphthyl, biphenylyl, anthracenyl, phenanthryl, and I groups are preferred. Further, the carbon number of the substituent 2 may be a monovalent heterocyclic group, which may be shielded from "1 to 4 (preferably j to 3 or i to 2) nitrogen atoms and oxygen atoms. Or a heterocyclic atom composed of a sulfur atom and having a ring of 3 to 8 members, preferably 5^8, preferably a ring of a monocyclic, polycyclic or condensed ring, such as a hydrazine group, a BenQ group, or a spray. , tamarind, triterpene, = = (lndQlinyl), (d), 丫, 咬, 嗜, 嗜 ' ' 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 吗 基Salivation of 'saltyl, benzoindolyl, (tetra)yl " stoppered sputum, sputum, trifilament, imi, benzo (purinyl), etc. Preferably, it is a phenyl group, a fluorenyl group, a thienyl group, and an oxazolyl group represented by the general formula [2]. The general formula of the present invention [U Γ 4 Γ can be, for example, benzene 4-diphenylaminophenyl group Isomer, 4~fluorophenyl, 4-cyanophenyl, to 5, 0; = from 1 to 1G of a burnt group, a carbon number of 1 atom, substituted by an aryl group having 6 to 12 carbon atoms 2319365 16 200806626 One or more substituents in the group of arylamine groups and cyano groups Substituted phenyl, 1-naphthyl, 2-naphthyl and the like naphthyl; 4-biphenyl; 9-phenanthryl; fluoren-9-yl; 4-pyridyl; 2-thiophenyl, etc. More specifically The preferred Ar2^ is exemplified by phenyl, 1-naphthyl, 4-biphenylyl, phenanthryl, wherein phenyl, bunyl or 4-biphenyl is preferred, and phenyl or naphthyl is preferred. The phenyl group is the most preferable. At the same time, as an ideal Ar3 & A 〆, although the ideal group of Ar2 to Ar4 as described above is exemplified, phenyl, 丨-naphthyl or 4-biphenyl is used. Preferably, it is more preferably a phenyl group or a naphthyl group, and a silk group is preferred. In the formula [2], Ar5 represents a carbon group having 6 to 18 carbon atoms which may have a substituent, and a carbon which may have a substituent The number from 2 to 3 至 is from the hydrogen atom, the (four) material or the one-valent heterobasic group, which is explained by the prevalent heterocyclic group. Here, the monovalent aromatic hydrocarbon group in Ar5 and the Ar2 are described. The monovalent aromatic hydrocarbon group to Ar4 is synonymous with a halogen atom, a halogen atom, or a iodine atom, such as a fluorine atom or a chlorine atom, R to R7, and a ruthenium atom, although there is no particular one. Monovalent fat a monovalent aromatic hydrocarbon group, a divalent aromatic group having a substituent, a monovalent aliphatic heterocyclic group having a substituent, a ketone group; a cyano group: a aryl group; , oxygen burning:; base::: dithiol, arylsulfonyl, etc.. fluorenyl carboxyl group, fluorene sulfonyl group, 319365 17 200806626 here as a monovalent monthly aliphatic hydrocarbon group, refers to carbon number 1 to One of 18 = The base of this mountain can be, for example, a linear one having a carbon number of 1 to 18 or a linear or branched alkenyl group having a number of 2 to 18, and a carbon to 2 to 18 # direct bond. a branched or branched block group, a carbon number 3 or a polycyclic or condensed ring type ring alkyl group. For example, methyl, ethyl, propyl, isopropyl 2 medin, isobutyl, dibutyl, tert-butyl, pentyl, isopentyl, and ;=, octyl, decyl, dodecyl, fifteen, and octadecyl, and an alkyl group having 1 to 18 carbon atoms. Human 2-propenyl 2-propan-1-one cyclopentane* Further, as a rare group, there may be mentioned, for example, a vinyl group, a propylidene group, an =isopropenyl group, a butenyl group, a 2-butenyl group, 3 -butenyl group, alkenyl group, diterpene group, octadecyl group and the like having a carbon number of 2 to 18, and as a block group, for example, an ethyl group, a block group, or a butynyl group , 2—Butyl, 3—Ding, Buxin, alkynyl, and octadecyl, and the like having a carbon number of 2 to 18. Examples of the cycloalkyl group include a decyl group having 3 to 18 carbon atoms such as a cyclopropyl group, a cyclobutyl group, a cyclyl group, a cyclooctyl group and a cyclodecyl group. The ε : 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 方 方 方 方 方 方 方 方 方 方 方The f*: valence ring aryl-, for example, phenyl, o-toluene carbon (tetra) ... - valence '::: benzene ... propyl phenyl and the like 'as a valence condensed cyclic hydrocarbon group, then, for example, naphthyl,八蔡319365 18 200806626 基,卜蒽基,2-蒽基,5_蒽基,卜菲基,9_菲基,卜苊美(l^cenaphthenyD, 2__ foundation (azulenyl), Buyouji, 2—triphenyl (triPhenylene) and the like: a valence condensed cyclic hydrocarbon group having a carbon number of 1 to 18, and a monovalent ring-forming hydrocarbon group, such as o-biphenylyl, m-biphenyl, a monovalent ring-forming hydrocarbon group having a carbon number of from 联 biphenyl, etc. Further, as a monovalent aliphatic atom heterocyclic ring I, it may be exemplified as containing 1 to 4 (1 to 3 or ! to 2) a nitrogen atom, an oxygen atom or a sulfur atom. It is a heterocyclic atom and has an early ring, polycyclic or condensed ring type aliphatic heterogeneous of 3 to 8 members (preferably 5 to 8 members). a ring group, such as pyrazolinyl "Cinnabar, N-Mercapin (ind.), 2-m〇rPhQlinyl, etc., such as a carbon number of 3 to 18-valent aliphatic Ring group. Also as a monovalent aromatic The base, the shell 1J may, for example, contain a hetero atom consisting of j to 4 (1 to 3 or ! to 2) nitrogen atoms, oxygen atoms or sulfur atoms and have 3 to 8 members (to 5 to 8 member _ is preferably an early 1, polycyclic or condensed cyclic aromatic heterocyclic group, such as trisal, 3%, stilbene, 2-brown, 3, fluorenyl, 2 sigh Benzyl, 3-tertyl, benzyl, bromo, transyl, benzyl, 3-mercaptopurine, 4-pyridyl, 2-pyridyl, 2,yl, 3-isoxazolyl 2, 塞口坐基 n塞唾基, 2_咪丝, 3—啦钱n琳基, 3-啥琳基, 4-啥琳基, 5-(四)基, 6—啥吓基, p奎Linki, 8_啥琳基, 卜异基基, 2-crocodile-like (2-Qui with aHnyi), 2-benzene-opening vasocarb, 2_benzoxenyl, N_^, and a number of 2 to 18-valent aromatic heterocyclic groups. 319365 19 200806626 Also, as an alkoxy group,

Alkoxy group to 8. Examples thereof include a methoxy group, an ethoxy group, a 〜, a thousand, a p, a flat i0 milk I, a propoxyoctyloxy group, a third octyloxy group, and the like, a carbon number j group, a naphthyloxy group, a 2-naphthyloxy group. And "as an aryloxy group", for example, phenoxy group, 4-tert-butylphenoxy

Further, examples of the alkylthio group include an alkylthio group having a carbon number of 丨 to δ such as a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group or an octylthio group. Further, as the arylthio group, an arylthio group having 6 to 14 carbon atoms such as a phenylthio group, a 2-methylphenylthio group or a 4-tert-butylphenylthio group may be mentioned. Further, examples of the substituted amino group include a fluorene-methylamino group, a hydrazine-ethylamino group, an anthracene, a fluorenyl-diethylamino group, an anthracene, a fluorene-diisopropylamino group, and a ν, ν_. Dibutylamine, anthracene-benzylamino, hydrazine, hydrazine-dibenzylamine, hydrazine-phenylamino, fluorenyl-phenyl-hydrazino-ylamino, hydrazine, hydrazine Amino, hydrazine, N-bis(m-tolyl)amine hydrazine, fluorene-bis(p-tolyl)amine, hydrazine, N-bis(p-biphenyl)amine, bis[4-(4 a substituted amino group having a carbon number of 2 to η such as a -methyl)biphenyl]amino group, a Ν_α_naphthyl-anthracene-phenylamino group, or a ν_-nyl-fluorene-n-ylamino group. Further, examples of the thiol group include an ethyl fluorenyl group, a propyl fluorenyl group, a pivaloyi group, a cyclohexylcarbonyl group, a benzamidine group, and a toluidine group (toluoy 1). Anisoy 1), cinnam〇y 1 (cinnam〇y 1) 荨 slave number 2 to 14 brewing base. Further, the alkoxycarbonyl group may, for example, be an alkoxycarbonyl group having 2 to 14 carbon atoms such as a methoxycarbonyl group, an ethoxycarbonyl group or a benzyloxycarbonyl group. Further, examples of the aryloxycarbonyl group include an aryloxy group having a number of 2 to 14 such as a phenoxycarbonyl group or a naphthalene 319365 20 200806626 'oxy group. Further, examples of the calcined sulphate base include alkanesulfonyl group having 2 to 14 carbon atoms such as a yttrium yellow base and a propyl fluorenyl group. "1" is an aromatic sulphate group, and examples thereof include a arylsulfonyl group having 2 to 14 carbon atoms such as a benzophenone sulfonyl group. The valence aliphatic hydrocarbon group and aromatics in the above R and R7. The hydrocarbon group, the aliphatic heterocyclic group, and the aromatic heterocyclic group may be further substituted by other substituents, and these substituents may be bonded to each other to form a ring, which may be a (tetra) atom. An aryl group, an alkoxy group, an aryloxy group, a arylthio group, a substituted amine group, a fluorenyl group, an alkoxy group, an aryl group: a base, a scutellite, an aragonite, and the like. The above is exemplified by the preferred examples in the general formula [2] of the present invention, and the 'preferably' is exemplified by, for example, a phenyl group, a 4-methyl group 4-fluorophenyl group, and a 4-fluorene group. Oxygen is also a sweet earth soil, a formazan base group, a 4-cyano group, a 4-phenylene group, a naphthyl group, a fluorene group, a base, and the like. The fluorenyl group represented by the general formula [2] of the present invention is as follows: "based group, 9,-methylphenyl) 3 0,"(fluorobenzyl)-3 decyl, 9 'U-methoxyphenyl) group, heart 2:, :) (43~ cyanophenyl) ten-base, 9~(... (2'-not)~3-carbazolyl, 9-(4 -biphenyl)-3-inoxazolyl, 9_(4_ mouth ratio σ疋yl)-3-portinyl hydrazine, 廿 is Q| base-: base is more base-- and more base is 9-benzene ; 2: 319365 21 200806626 bis. on the extension of biphenyl represented by the general formula [3]. One of R2 ° to R24 and one of R25 to R29 - the main R represents the chlorine atom, _ 辛 atom Γ Γ The linkages 'the rest are independent of a homologous atom or an organic residue. The dentate atom or the valence organic residue in R to '29 is synonymous with the dentate atom or monovalent organic residue as taught in the above h. To the sub-, the adjacent organic residues may also form S with each other. In the general formula [3], the one of n r24 and R25 are bonded, and the extended biphenyl group is formed. There is no particular limitation on the position of the bonding bond (8) when the biphenyl group is extended, it can be 2, 2, and 2, 4, 4, -extended biphenyl, ? q, From "earth 3, 3 extended biphenyl, hydrazine%, 2, 3 - extended biphenyl, 2 extended biphenyl, etc.. Stretched as base, 3, 4, - among these combinations, county LV d2G Λ心5 Sa 1 its inflammation ^ a " R is the binding bond of 4, 4, - extension = is '. This is because the higher the symmetry of the molecule, the heat resistance, Tg value, and The more you return ^ p»B. d19 It is also easier to synthesize the compound. Among the K26 to R28, the heart...", and the unbonded bond (4) / its "example" can be cited as hydrogen atom, carbon number In the case of these substituents, the phenyl group is also small in the molecule, and is easily formed by vapor deposition or the like, and is also preferable in terms of stability. When Shihwa is more tolerant = time ^ money of general formula (4). Show hydrogen material in, or pay for organic residues. UI you h ^ π ary material or - machine silk, * the above mentioned in the opposite The K to G atom or the monovalent organic residue is synonymous. 319365 22 200806626 Also, 1^ and R31, "with R33, ruler 34 and r35, or r36 and r37, between the substituents Combine with each other to form a ring. [5] R38 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having a number of 1 to 3, a carbon number 6 to a monovalent aromatic hydrocarbon group which may have a substituent, or a carbon number which may have a substituent a monovalent heterocyclic group of 2 to 5, wherein the alkyl group having an inverse of 1 to 3, an aromatic hydrocarbon group having 6 to 12 carbon atoms, and a one-valent heterocyclic group having 2 to 5 carbon atoms are exemplified as ^ To the carbon number of the phase in the one-to-one organic residue term of R7. Further, the substituent ' which may be possessed may be, for example, the aforementioned atom or a valence organic residue. ^ Particularly desirable examples include, for example, a gas atom, a phenyl group, a biphenyl group, a methyl group, a xylyl group, or a methyl group, an ethyl group, and a gas. Here, the 30-position of the formula [2] is It is more preferable that r^r7 is a chlorine atom. In this case, when the structure is obtained, the molecular weight is also superior in terms of secondary properties when the compound (material) is sublimated by steaming or the like. Moreover, in the general formula m, "the structure of the general formula [5] is further described below. The generality of the three-seat base having the general formula (2) is generally "the card compound is not a bond." The compound of the knot has a tendency to have a structure of _, and the hot shirt - the base is private (refer to the next 319365 23 200806626)

In the squat compound, although a ruthenium-alkyl compound in which an alkyl group is coordinated at another bonding position of nitrogen is well known, a compound of the present invention is a substituent bonded at this position. (=Ar5) is an aromatic group or a hetero-fragrant group. The aromatic group or heteroaromatic group has a greater effect of improving the stability, and in the case where Ar5 is in the general formula [5], it is expected that the effect of improving the stability is generally discussed in the third position. effect. The nitrogen atom:: takes a sub-supplier and acts 'but with respect to binding. This may be because (4)# has a supply of substituents, which makes it difficult to accumulate with nitrogen atoms. On the other hand, since the soil is formed in the third position, the planarity of the plane structure is relative to the benzene and the flavor of the money. This clothing can form an electronic supply (refer to the following 319365 24 200806626)

Since the substituent on the nitrogen atom does not form a plane with the taste ring, it does not become an electron supply body. Since the planar structure can be obtained with respect to the loop of the carbazole ring, it becomes an electron supply. Therefore, the σ card in the present invention is included. In the amine compound, the amine group bonded to the carbazole ring and the nitrogen atom of the oxazole ring are both electron donors and may exhibit phenylenediamine An electronic supplier effect with the same or higher structure (refer to the following formula).

For this reason, the yttrium-containing amine compound of the present invention is likely to be a compound having a small ionization potential (a compound having a higher energy level than a matrix state of an organic molecule), and an organic EL is produced. In the case of a device, a compound having a high hole injection property can be formed. Furthermore, it is combined in the third place. The catal ring has a lower molecular crystallinity due to its lower molecular symmetry than the carbazole ring bonded to the nitrogen atom, and may have stability for forming a film due to an increase in amorphousness. There are many contributions to improvement. 25 319365 200806626 Two siramine compounds, because they only have --sex, the fruit is not asymmetry, so it can improve the amorphous material fiM± + #4... crystallization. When used as an organic EL element d rk _t), the life of the organic EL element can be extended. The base A in the 尤 Π is 4, 4, - 伸萨 | its ^ ^ life is significantly extended. %本•' can make organic EL components only guide! According to the invention of the second invention, the amine compound is prepared by the sublimation method in comparison with the dicarbazole compound in the molecular neutron amount: °. At the time, it is possible to use a lower, w two = Qian system, so for organic materials = easy to refine. That is, the compound is also pregnant, and it is better to use "00 to ... and 5, i,500 or less as the following hi i, 200 or less is better, and 1 or less is better. . This reason is due to the fact that the vaporizability at the time of the element may be deteriorated. When the organic electroluminescent element is formed by the steaming clock and the amount is made into an organic electroluminescent element, the present invention: the vapor deposition in two cases Sexually, there may also be a harmful compound of the evil organic compound. The amine compound of the cardinal is made for the cloth method in the steaming of the clock::, machine: the solubility is also high, and the organic layer or the organic layer* metal In the organic layer of the electric material, there is Joule heat generated between I and the electrode of the 319365 26 200806626 • Resistance (heat resistance), so it can exhibit high luminous efficiency when used as an organic EL element material. It also helps to make it glow for a long time. Representative examples of the compound of the present invention are shown in Tables 1 to 3 below, but the present invention is not limited to the scope of these representative examples. 27 319365 200806626 -[Table 1] Compound Ar1 Ar2 Αχ8 Ar4 A (1) -ο ο -ο ^ΟΌ- (2) -ο -ο -οο (3) ο ~ο -οο (4) -Ό -οο- (5 A -οο -οο -οο (6) ~ο -ΟΌ (7) Ο -Ο -ο-ο (8) -8 (9) Xi^ -ο δ δ -οο 28 319365 200806626 -[Table 2] do 4 ~〇-〇〇(11) -〇% 〇〇~ (12) 〇〇- (13) ~Q) ~〇^ <y〇r (14) 〇-〇〇(15) 4 〇-〇 <} 〇〇(10) ~〇.乃<xy (17) 2 -〇〇〇<κ> (18) *〇〇~〇-〇〇- (19) 4 -〇〇-〇-οο- ( 20) -〇-〇29 319365 200806626 [Table 3] (21) -〇-〇〇〇(22) 〇~〇-〇(23) 〇χ^ο (24) -〇-〇〇命(25) - 〇〇p<5 (26) 〇(27) -〇〇(28) -Ό -〇~〇(5-p (29) 4 〇-〇-CH> (30) 4 -〇-Ό 30 319365 200806626 • The preferred salivary amine compound of the present invention may, for example, be a compound: the base A in the general formula [1] is 4,4,_extended biphenyl, and is 9-phenyl-3-(tetra) Base; p to Ar' are independently It is a group of diarylamine groups, acne atoms, or an aryl group which may be substituted with an alkyl group selected from carbon number: 5 to 5, an alkoxy group having 1 to 5 carbon atoms, a mermine substituted with 6 to 12 carbon atoms, or an aryl group. a phenyl group, a naphthyl group, a 2-naphthyl group, a 4-biphenyl group, or a 9-phenanthryl group substituted with the above substituents in the group. Preferred oxazole-containing amine compounds of the invention may be, for example, a Compound: The base in the formula (1) is 4, 4,-biphenyl, and ΑγΓ is a phenyl-3-sodium sinyl group. Ar2, red 3 and Ar4 are each independently a phenyl group, a bupropion group, a 2-naphthalene group. Further, the biphenyl group-containing compound of the present invention may, for example, be a compound: the group A in the formula (1) is 4,4'-biphenyl group, and the group is 9-phenyl group. 3_ Leica sulphate, ", red 3 and ^4 are each independently phenyl; [-naphthyl, especially phenyl. The salivary amine-containing compound of the present invention can be applied to various uses. It can be used as a performance sensitizing effect, a heating effect, a coloring effect, a fading effect, a light storage effect, a phase change effect, a photoelectric conversion effect, a photomagnetic effect, a photocatalytic effect, an optical frequency conversion effect, an optical recording effect, a free beauty effect, and the like. The functional material, or conversely, can also be used as a material having an illuminating function as a receiving effect. The luminescent material, the photoelectric conversion material, the light and the second can be exemplified by, for example, the tens of 屺 屺 屺 枓 、, image forming materials, ph〇tochromic materials, organic EL materials, photoconductive materials, di-free radicals Producing material, acid generating material, alkali generating material, first material, nonlinear optical material, second high frequency wave generating material 3 frequency wave generating material, photosensitive material, light absorbing material, near infrared absorbing 319365 31 200806626 (4), silk Burning hole effect (10). t_emiGal hQle bur material, light sensing material, #w分#, g; material ^ ^ first cover material, sensitization material for photochemotherapy, optical phase, cross-linked recording material, dyeing for mechanical therapy of well-fall line ^ Among the various applications in which the recording material, the magneto-optical recording material, and the light are used, it is particularly preferable to use it as a material for the branch L (material for organic EL or material for organic EL element). It is used as a material for organic EL elements as a high-purity material, and it is required to be inserted in the sound of ^, 匕 /

In the case of Tt, the carbazole-containing amination of the present invention can be hunted by sublimation purification or recrystallization, re-slaught method, zone melting method, column purification method, adsorption method. Etc., or these parties, and combine to refine. In these refining methods, it is more recrystallized>; In the sublimation-requiring compound, in the sublimation refining by the sublimation refining method, it is preferred to maintain the sublimation bottle at a lower temperature; in the temperature of the compound of the target, the sub-sublimation is performed in advance. It is preferable to apply a temperature gradient to the portion where the sublimate is collected, and to disperse the impurity into an impurity and a target. The sublimation purification described above is a purification for separating impurities, and is suitable for use in the present invention. Further, it is also possible to predict the evaporability of the material by ordering the foreign refining. Here, an organic EL device which can be produced by using the carbazole-containing amine compound of the present invention will be described in detail. The oral EL element is composed of an element forming one or more layers of one layer between the anode and the cathode, and the one-layer type organic EL element means a member formed only by the light-emitting layer between the one pole and the cathode. . On the other hand, the multilayer germanium organic EL element means that in addition to the light-emitting layer, the hole or the electron capacitor 319365 32 200806626 is easily injected into the light-emitting layer, or the hole and the electron are made in the first place. The layer is smoothly smoothed again: the mouth is formed as a purpose (4) to form a hole in the hole, a hole in the hole, a hole in the hole, and a layer to form a layer. Therefore, the multilayer organic component constitutes ' It can be considered that it is composed of a plurality of layers as follows: (1) anode to injection-emitting layer, (2) hole injection layer/hole transport layer/light-emitting layer, (3) anode/hole injection layer, light-emitting layer, electron Injection layer, cathode, (4) anode/hole injection layer, hole transport layer/light-emitting layer/electron injection layer/cathode, (5) ~pole/hole injection layer/light-emitting layer/hole stop layer/electron injection cathode, (6) Anode/hole injection layer/hole transmission: ... electron injection layer/cathode, (7) anode, light-emitting layer, electric layer/electron injection layer/cathode, (8) anode/light-emitting layer, electron injection cathode and the like. Further, each of the above organic layers may be formed of two or more layers, respectively. In this case, there has been a proposal for a so-called "multi-photon emission" component in which a plurality of layers of the above-described multilayer organic rainbow element are multilayered in order to improve light extraction efficiency. . Taking this as an example, the charge generation can be made in an organic EL element composed of a glass substrate/anode hole transport layer/electron transport light-emitting layer/electron injection layer/charge generation layer/light-emitting unit/cathode. A method of performing a plurality of layers on a layer and a portion of the light-emitting unit. The carbazolyl-containing amine compound (organic electroluminescence device = material) of the present invention can be used for the layer formed as described above, but is particularly suitable for use in an electroluminescent layer, a hole transport layer, and a light-emitting layer. Meanwhile, the organic 319365 33 200806626 of the present invention may be a compound which can be used alone, but a combination of a compound of more than one type may be used, or may be used in combination. Further, in the above-described hole injection layer, hole transport layer, and calender layer, it may be used together with other materials. In the hole injection layer, it is possible to use an electroluminescent injection layer to exhibit an excellent hole injection effect, /, and a hole injection excellent in _ and film formation, and a multi-layer lamination and a high hole injection effect. Material and hole transfer = When laminated, the material that can be used separately is called hole injection / : can, = material. The material for an organic electroluminescence device of the present invention is suitable for use in a hole injecting material, a hole in a hole in a hole injection material, or a hole in a hole. This === At the electric field strength, the hole can be transported to the material of the Γ 至 2 to = 2 plus - the electric field - the electromotive is preferably / ί / sec. Other hole injection materials, life and fats which can be used in combination with the organic dry and sturdy materials of the present invention can be obtained from the ideal properties described, that is, those without special materials or organic materials. It is used to charge the wheel as a hole. Any of the well-known people used in the hole injection layer of any piece == two materials or hole transport materials, in particular, can be listed as biological (芩知吴国专利3, 丨89, 447 manual 319365 34 200806626. etc. ), a pyridin derivative (refer to Japanese Patent Special Publication No. Sho. No. 6), and a compound formula derivative (refer to U.S. Patent No. 3,615, the specification of the operation, the specification of the U.S. Patent No. 3,820,989, and the specification of U.S. Patent No. 3,542,544 Japanese Patent Publication No. 45_555, Japanese Special Japanese Knife '51_ϊ〇983, Japanese Unexamined Gazette No. 93224, Kaikai.nm, and Japanese Unexamined Gazette__ ZHAO 55 — _7, 曰本特开昭 55-娜3号, 曰本特开昭56-36656, etc.), (4) Lin derivative and 吼_ (py-e) derivative (refer to US patent) 3, deputy, (4) manual, US patent 4, 2 7 8 7 4 · β deficiency % μ **, b 唬 明 明 , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , JP-A-49-1〇5537, JP-A-55-51_, Japanese Special开 56 - - - - - - - - - - - - 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎 虎And a phenylenediamine derivative (refer to the specification of U.S. Patent No. 3,615, 4G4, Japanese Patent Publication No. 5 pp. 1〇1〇5, Japanese Patent Publication No. 46-3712, Japanese Patent Publication No. Sho 47-25336, Japan, Japan JP-A-54-53435, JP-A-54-U, K.K., Japan (4) Sho. 54-1, 19925, etc.), aryl (4) organisms (refer to US Patent No. 3,567,45 (), US-specific = 3' 180' 703 6 brothers, U.S. Patent No. 3, 24, 59, No. 3,658,52, Lang, U.S. Patent No. 4, '232'103, U.S. Patent No. Japanese Patent No. 4, 175, 961, US Patent No. 4' 012' 376, 曰本特公昭49_357〇2号 319365 35 200806626, Japanese Special Public Show No. 39-27774, Japanese Special Open No. 55-14425 〇, Japan JP-A-56-1 1 9132, JP-A-5-1-6-22437, West German Patent No. 11, 11 (), No. 518, etc.), an amine-substituted chalcone derivative (refer to US Patent No. 3,526,501, etc.), a salivary derivative (refer to US Patent No. 3) , 257, 203, etc.), styrene-based onion derivatives (moxibustion, 曰本特开昭56-46234, etc.), and 嗣 derivatives (see 曰本:::丨广3 7 No. bulletin, etc., 腙 derivative (refer to U.S. Patent No. 55 ^ ^ 33 54-^143 ^ . 9 ^ Japanese Special Open Day D 55-46760, Japanese Special Open No. 55 - Dai Na No. Kaizhao 57_1135G, Japan's special opening 5, i4, 曰, 曰 特 特 2 2 2 2 2 2 2 2 、 、 、 、 、 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( (曰本特开昭心1:^ΤΓ61'72255 ^ Newspaper, 曰本特开昭62韵74号公告, 62-1 0652 bulletin, Japan special open Japanese knives R9 plus Japan 4 inch open Zhaokai Zhao _455 Bulletin 'Japanese U=l2n55 bulletin, Japan special 60-174749 9 ^ 9 newspaper, etc.), money is silazane) Yan f day 13 6 (M75G52 No. 4,950, coffee number book & ^^^^ country patent number Magic conductive aniline copolymers (Japanese Patent Publication said present said this Bu Publication No. 21 1399 disclosed the + = 319 365 son oligonucleotide 36200806626-- oligomer (particularly a thiophene oligomer) and the like.斜 oblique, life Γ use the above materials as a hole injection material or hole transport;,, 'can use the porphyrin compound 63-295695 bulletin, 芸乐a __ inch 幵Ί mouth into the object ί The old Ira quinoa, the amine compound and the styryl amination 53-27033 ^, ^ J;;;; " 4 p.fl77 ^ Sakamoto Kaikai 54-58445, Japan special π 7/ Unexamined 54-64299, 曰55~144250^^ f Lubiao 119132, and Japanese Unexamined 61-295558 #"报, 曰本特开昭61_98353号,日本特昭昭63 -295695, etc.). Example Ψ ^ v yak, for example, Wu Guo patent 5, 061, 569 = 4, 4, - double (n_ (b*) containing two condensed aromatic rings in the molecule ))-N-phenylamine)biphenyl, etc., or reported by the triphenylamine unit I cost = flat: 308688 gong Φ ΛΛ 4 ,, . dry %, σ into two star bursts ( Star burst) Etc., =, 4/tea (8) (3~methylphenylphenylamino) triphenylamine or air enemies 2 Γ List copper (iv) (e°PPer this (10) We) Hole injection material. In addition, other J The Fangxiang dimethylene compound and the organic compound are used as materials for the non-abandoning material or the hole-carrying material of Ray 1 Sl, P-type SiC, etc. The base -N, r makes it a stupid; the system can be exemplified by, for example, N, N, _ N NNN, NW - biphenyl hydrazine 4, - diamine, ,:, N"-(4-methylphenyl hydrazine, !, n, n? -ca ® ^ ^ x , January female diphenyl "local hydrazine, hydrazine, phenyl ~ 4,4,-diamine, U, - soil, - one Nylon - 1,1 ,-biphenyl fluorene 4,-dimoonan, N,N,-(a 319365 37 200806626 phenyl)-N,N,-(4-N-butylphenyl)-phenanthryl-9,1 〇-diamine, n,N-bis(4-di-4-methylaminophenyl)-4-phenyl-cyclohexane, N,N, a bis(4-diphenylamino-4 -biphenyl)-N,N,-diphenylbenzidine, N,N, bis(4-diphenylamino-4-phenyl)-N,N,-diphenylbenzidine, N , N, a double (4-diphenylamino-4-phenyl,-bis(indenyl-naphthyl)benzidine, N,N-bis(4'-phenyl(1-naphthyl)amino)- 4-phenyl)-N,N,-diphenylbenzidine, N N-bis(4'-phenyl(1-naphthyl)amino-4-phenyl)-N,N,-bis(1-naphthyl)benzidine, etc., which are used for hole injection materials and holes Any of the materials to be transported. ^Electrical/same/main material and hole transporting material used together with the compound of the present invention (material for organic EL element), the following general formulas [6] to [11 can be used. a compound. General formula [6]

(wherein R is an alkoxy group, or cyanide to Ra each independently represents a hydrogen atom group', but not all of them are simultaneously a hydrogen atom). Butoxy, tert-butoxy, octyloxy, third (2-borny 1 , third butoxy, octyloxy, third octyloxy, 2 borneol, propoxy, borneoloxy

Here, the alkoxy group may, for example, be a methoxy group or an alkoxy group of 18. The ideal combination of RaU to Ral4 is all methoxy, ethoxy, a red animal λ 319365 38 200806626 ‘general [7]

(wherein Z21 is a linking group, and the table represents a monovalent aromatic hydrocarbon group). The scooping person R η is exhausted and stupid is Fiji::. : 4 er, 2, " Cai Ji, Ji", 40: two Asians with a single bond, stretched women's base, pair - stupid naphthyl, 2 off: soil again, n Ra26 is selected from phenyl, 1~ Aromatic phenylbiphenyl, m-biphenyl and p-biphenyl 1 formula [8]

In the bond or divalent aliphatic hydrocarbyl hydrazine, Z31 is a linking group, an aromatic hydrocarbon group, an oxygen moon early, /, an early %, a cation milk supply segment, and a divalent standing site representing a monovalent aromatic hydrocarbon group: By. R Μ separate link base 'is a single bond, vinyl extended, o-phenylene, 319365 39 200806626 • phenyl, p-phenyl, 1,4-naphthyl, 2, 6- The naphthyl group, the 9, ι〇- phenanthrenyl group, and the 9, 10-extended fluorenyl group are preferred, and a single bond, an ethyl group, a p-phenylene group, and a 1,4-naphthyl group are more preferred. Further, Ra31 is preferably a monovalent aromatic hydrocarbon group selected from the group consisting of a phenyl group, a 1-naphthyl group, a 2-naphthyl group, an o-biphenyl group, a m-biphenyl group, and a p-biphenyl group. General formula [9]

(wherein R SR is independently a monovalent aromatic hydrocarbon group). R to Ra48 is preferably a monovalent aromatic hydrocarbon group selected from the group consisting of a phenyl group, a naphthyl group, a 2-naphthyl group, an o--phenyl group, a m-biphenyl group, and a p-biphenyl group. General formula [10]

(wherein, Ra5 to Γ56 each independently represent a monovalent aromatic smoky group). The 56 is preferably a monovalent aromatic hydrocarbon group selected from the group consisting of soil 1 not I 2 naphthyl, o-biphenyl, m-biphenyl and p-biphenyl. General formula [11] 二土 ’, ,, 土 0 319365 40 200806626

(In the formula, Ra61 to Ra64 are respectively called 1±, and the integers of 1 to 4 are also shown). , Japanese Japanese hydrocarbon base, p-table

Ra61 to Ra64 are monovalent aromatics selected from the group consisting of phenyl, 1 - drum, Η 秘 Λ 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜 斜The smoke base is better. The compound represented by the general formula [6] to [丨丨] described above on X is particularly suitable as a hole injecting material. Tables 4 to 7 below show particularly desirable examples. ^ 319365 41 200806626 [Table 4] Chemical Structure of Compound HIM1 p Q ^ ^ 0 HIM2 _ p G ^ Qr( Q Ο HIM3 oP 亡 Death HIM4 GQ 〇-<: 3-0 Q Ο \ /=\ /=\ 42 319365 200806626 [Table 5] HIM5 qp Register l HIM6 {yP RO Q 0 HIM7 QQ ύ o HIM8 p Q ΟΛ: Q Ο PQ b fflM9 43 319365 200806626 '[Table 6] HIM10 Οτό )ζΧ) HIM11 Q Ρ HIM12 HIM13 HIM14 Q Ο 44 319365 200806626 Μ表7]

Further, examples of the hole transporting material which can be used together with the compound of the present invention (material for organic EL device) include the compounds shown in the following Tables 8 to 14. 45 319365 200806626[Table 8] Compound Chemical Structure HTM1

—N

HTM3

HTM4

46 319365 200806626 ‘[Table 9]

47 319365 200806626 •[Table 10] HTM9 d^b HTM10 QP SO ob _p o ύ ^ HTM11 _ OQ _ cP-h 0N^3 ό b HTM12 ^-o Q 0 Q^w^P HTM13 3^-00 ό ό ^<χ>-ζ ό t> 48 319365 200806626

49 319365 200806626 , [Table 12] HTM18 HTM19 ryP ob 0 〇0 ^ HTM20 ΡΗ» , -σΡ . 0 0 q^w^pd^b HTM21 oP ^-o ^ 0 Q/=vrvP (HaC^C ^qCHah 50 319365 200806626 _ [Table 13]

51 319365 200806626 ' [Table 14]

When the hole injection layer is formed, the chemical substance can be thinned by a known method such as a vacuum ruthenium plating method, a spin coating method, a casting method, or a lb method, but the hole is formed. The film thickness of the injection layer is not particularly limited and is usually 5 nm to 5 # m. On the one hand, an electron injecting material can be used in the electron injecting layer: two or two pairs of light emitting layers exhibit excellent electron injecting effects, and can form an electron excellent in adhesion to the negative sample I and film formability. Inject the layer. Examples of such an electron injecting material include, for example, a metal complex compound, a nitrogen five-membered ring derivative containing 319365 52 200806626, a biological, a 蒽m street organism, a diphenyl dynasty (dlPhenoquinone) derivative, and a dioxide (plus Yan Qing (10) he) derivatives, 8 four (four) derivatives, sub-smoke derivatives, oxime derivatives m (SilQle) derivatives, oxidized triarylphosphine derivatives, ethyl acetate, sodium acetate and so on. Further, although inorganic/organic composite materials such as a metaphysical metal doped into a bath phenantphenanthine (bath〇phenanthr〇1) may also be cited (Collectives of the Polymer Society, Vol. 5, No. 4, 66) Leap year release), or the 5th application physics association joint lecture speech draft, N. - 3, 14G2, and B_, TPP, T5MPyTZ, etc., which are described in the 2nd year, are examples of electron injecting materials. However, as long as it is a film that can form a film necessary for forming a device, and can inject electrons from a cathode and transport electrons, there is no special. limits. Among the above electron injecting materials, particularly useful electron injecting materials are, for example, metal complex compounds, nitrogen-containing five-membered ring derivatives, sulphur (Silole) oxime, and oxidized triarylphosphine derivatives. The desirable metal complex compound which can be used in the present invention is suitably a metal complex compound of 8-hydrocarbylquinoline or a derivative thereof. Specific examples of the metal complex compound of 8-hydroxyquinoline or a derivative thereof include, for example, ginseng (8-hydroxyquinolinic acid) aluminum, bismuth (2-mercapto-8-hydroxyquinolinic acid) aluminum. , ginseng (4-methyl-8 hydroxyquinolinate) aluminum, meal (5-methyl-8-hydroxyquinolinic acid) aluminum, ginseng (5-phenyl-g-hydroxyquinolinic acid) aluminum, double (8-hydroxyquinolinic acid) (1-naphthol (1-naph1±〇late)) aluminum, bis(8-hydroxyquinolinic acid) (2-naphthol) aluminum, bis(8-hydroxyquinoline) (Phenolate) aluminum, bis(8-carbamic acid) (4-cyano-1 -naphthalene) aluminum, bis(4-methyl-8-hydroxyquinoline) (i-naphthol) Aluminum, bis(5-fluorenyl-8 hydroxy 53 319365 200806626 • quinolinic acid) (2-naphthol) aluminum, bis(5-phenyl-8-hydroxyquinoline) (phenol) aluminum, double ( 5-cyano-8-hydroxyquinoline) (4-cyano-1-naphthol) aluminum, bis(8-hydroxyquinoline) aluminum chloride, bis(8-hydroxyquinoline) (o- Indole phenol) aluminum complex compound such as aluminum; ginseng (8-based phthalocyanine) gallium, ginseng (2-mercapto-8-carboxylated acid), ginseng (4-mercapto-8-) Kiva|acid) gallium, ginseng (5-mercapto-8-hydroxyquinoline) gallium, ginseng (2-methyl-5-phenyl-8-hydroxyquinoline) gallium, bis (2~ 曱(8-hydroxyquinolinic acid) (1-naphthol) gallium, bis(2-indolyl-8-hydroxyquinolinic acid) (2-naphthoquinone) gallium, bis(2-indolyl-8-yl)啥兮, bis(2~ decyl-8-hydroxyquinoline) (4-cyano-1-naphthol) gallium, bis(2,4-dimethyl- 8-hydroxyl) Quinolinic acid (1-naphthol) gallium, bis(2,5-didecyl-8-hydroxyindole | acid) (2-napan), bis (2-indolyl-5-phenyl-8) - 噎 噎 琳 琳 琳 琳 琳 琳 琳 琳 琳 琳 琳 琳 琳 琳 琳 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 镓 2- 2- 2- 2- 2- 2- Gallium complex compound such as fluorenyl-8-hydroxyquinoline) gallium chloride, bis(2-methyl-8-hydroxyquinoline) (o-indophenol) gallium; others such as 8-quinoquinoline Lithium acid, copper bis(8-hydroxyquinolinate), manganese bis(8-hydroxyquinolinate), bis(10-hydroxybenzo[h]quinolinate) oxime, bis(8-hydroxyquinoline) A metal complex compound such as zinc or bis(10-hydroxybenzo[h]quinolinate) zinc. Meanwhile, in the electron injecting material which can be used in the present invention, as an ideal nitrogen-containing five-membered ring derivative, for example, a carbazole derivative, a thiazole derivative, an oxadiazole derivative, a thiadiazole derivative, a triazole can be cited. The derivative may specifically be, for example, 2,5-bis(1-phenyl)-1,3,4-carbazole, 2,5-bis(1-phenyl)-1,3,4-thiazole, 2 ,5-bis(1-phenyl)-1,3,4-diazole, 2-(4,-tributylphenyl)-5-(4,-biphenyl)-1,3 , 4-oxadiazole, 2,5-bis(1N-methyl)-1,3,4-oxadiazole, 1,4-bis[2-(5-phenyl-diazolyl)] stupid, 319365 54 200806626 .Based 'disalyl} + tert-butyl]benzene, 2_(4'-third basic) j(4,,-biphenyl)-U,4-anthraquinone, 2,5 - bis-1,3,4-thiadiazole,]4_雔"?α* (1Nyl)--丁其#宜,,和[2 (5_本基thiadiazolyl)]benzene , 2-(4,-:dibutylcarbyl)-5-(4,,_biphenyl)_u, 4-tris-s, 2,5-naphthyl)-1,3,4-triwax, 1, 4_Double [2_(5_Benzene)] benzoic acid and other electron injecting materials can be used as an ideal enthalpy: The following general formula is called, di-salt-general formula [12] r1 (wherein 'ΑγΓΪ and Arr2 分Κιί 想士士一香HH strict ^ can have a substituent of a monovalent aromatic 曰 rank 4 base or 彳A shell-containing murine aromatic heterocyclic group. - a valence-containing II aromatic heterocyclic group, which may, for example, be a 21-Butidine, a fluorenyl group, a 4, a bite group, a 3-tower cultivating base, or a quinone diterpenoid, 5 +定定, 2 — _基基基 41 Aromatic heterocyclic group; 2,基—=,7,yl,8,yl,2_噎_yl, 4:^, yl, lenyl, 2, wood Base, 5_ box base, 丨 丨 科 坐 — — — —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— —— - base, 4, 4, _. More than bite_2_yl, $*, decyl, etc.; valence, aromatic heterocyclic group; and, these: valence = hydrogen atom on the thiol group, also via a valence aliphatic hydrocarbon group or a 319365 55 200806626 Replaced by a volatile aromatic group. As Arr] and Arr2, the preferred one is a fluorene-based aliphatic hydrocarbon group or a monovalent nitrogen-containing aromatic hetero-group, and the hydroxy group is, for example, 1-caiji, 2-caiji, or adjacent _"|= Substituted by jin, for example, phenyl; and, preferably, one of the deuteriums ^ between bis-biphenyl and p-dihydroalkyl or monovalent aromatic:::: no heterocyclic group, also _4_基。 A 2 _ such as pyridin-3-yl and 2, 2, - are the following 'in Table 15 to 】 specific examples of only the main one derivative. The oxadiazole which can be used in the present invention 319365 56 200806626 -[Table 15] Chemical structure of the compound EX1 0~0~t:^Q*c(cH3>3 EX2 Q Ο X EX3 QP x=/ N_N EX4 P(CH3)3 Q 0 57 319365 200806626 -[Table 16]

58 319365 200806626 _ [Table 17] EX10 Ο Q EX11 o q EX12 q p EX13 q p EX14 Q Ο 59 319365 200806626 ▲·[Table 18]

(wherein, Ar and Art2 each independently represent a pharmaceutically aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group), and a aryl group of a substituent, wherein Aru and a/2 represent, for example, a phenyl group, a naphthyl group, It is thought of a !5 aromatic hydrocarbon group, which may be listed as a biphenyl group, etc., which is substituted with a benzyl group, a m-phenyl group, or a nitrogen-containing aromatic heterocyclic group. Further, the::,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 4 - The US-inhibited aromatic heterocyclic group can also be substituted by the -valent fat side of these - valence nitrogen. In addition, the ideal monovalent value in Art3 = 仏 aromatic surface hydrocarbon group such as phenyl, naphthyl, 2_caiyl, o-, hydrazine, =^ listed biphenyl, these -valent aromatic hydrocarbon groups can also be fine The base group and the p-valent nitrogen-containing aromatic heterocyclic group are substituted. Further, the phenanthrene group or the nitrogen-aromatic heterocyclic group may, for example, be an ideal valence-containing pyridyl group. Fixing the base, etc., this also - the price of 礼 夭 夭 疋 疋 疋 、 3 3 3 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 疋 3 3 3 3 3 3 3 3 3 3 3 3 3 3 "Used; 319365 61 200806626 % [Table 19] Compound chemical structure ET1 Ph ET2 Q , P ET3 CH3. Q 0 Ο ET4 P(CH3)3 Q , 0 62 319365 200806626 '[Table 20]

63 319365 200806626 ‘·[Table 21]

ET10 Q ^ Q ET11 Ο Q ET12 Q . , P Ch-^t-rO ET13 Q , . P ET14 Q . . P 64 319365 200806626 [ Table 22 ] ET15 Oph phO ET16 Q , , PV/ ET17 pq ET18 Q . P ET19 pq 65 319365 200806626 '·[Table 23]

Further, among the electron injecting materials which can be used in the present invention, a particularly preferable silole derivative is, for example, a Silole derivative represented by the following general formula [Μ]: , and the general formula [14]

Ar^ Αγ^3 A^2 «r Ari>1 rp2〆, RP1 (wherein H r2 independently represents a pure group having a substituent, a -valent aromatic smoki group or a monovalent nitrogen-containing aromatic heterocyclic group ; 至 to = respectively represent a monovalent aromatic smo-containing nitrogen-containing aromatic heterocyclic group which may have a substituent; and RP2, ArP1 to Ar = may be linked to each other (tetra) to form a ring). Phase 4 can be: Hey! 2. As RiRP2, an ideal monovalent monthly aliphatic hydrocarbon group, also substituted with a fluorene aromatic hydrocarbon group or a monovalent nitrogen-containing aromatic heterocyclic group, such as a base, an ethyl group, a propyl group and a butyl group; A hydrocarbon group, which may also be a monovalent aromatic, a samarium or a monovalent nitrogen-containing aromatic hybrid, may be exemplified by a phenyl group, a f-phenyl group, and a Further, as an ideal-valent nitrogen-containing aromatic heterocyclic group, it may be substituted by a valence 319365 66 200806626 base or a monovalent aromatic hydrocarbon group, and examples thereof include a 2-pyridyl group, a group and a 4-(tetra) group. . Further, as ArP1 to a, a preferred 〜=== group hydrocarbon group may be substituted by a monovalent aliphatic hydrocarbon group or a monovalent nitrogen-containing aryl group, and examples thereof include a phenyl group, a b-ion 9^^^,隹Nanyl, 2-naphthyl, ortho-biphenyl-biphenyl and p-biphenyl; and, as an ideal, valence-containing heterocyclic group, may also be a valence aliphatic hydrocarbon group or The monovalent aromatic group can be exemplified by, for example, 2-acridinyl, 3-pyridyl, fluorenyl, 4-pyridyl, 2, 2, ~bipyridin-3-yl and 2, 2' -bipyridyl~4~yl. Hereinafter, Tables 24 to 28; in the present invention, specific examples of the Silole derivative can be used. 319365 67 200806626 ’·[Table 24]

68 319365 200806626 *.[Table 25] ES5 Q〇PP h3c', ch3 ES6 Q Ο ES7 op ES8 QOPP <ys<) 0Ό ES9 GO 0~0^MI^~0 σο 69 319365 200806626 '·[Table 26] ES10 op a ES11 响 ES12 qp N===^^Siv^~NNJ OD ES13 op ES14 qqpp 03⁄4 70 319365 200806626 •[Table27] ES15 QP_ „ ES16 ES17 Cn Q Ο O 03⁄4 ES18 op ΟΟΛ^ΗΙ ES19 oo 71 319365 200806626 . [Table 28]

O-P-Ar^

/U = medium to W, respectively, independently indicates that it may have an aromatic hydrocarbon group). Here, as the W to π, an ideal valence aromatic smog group may be substituted by a "(iv) aliphatic hydrocarbon group or a valence nitrogen-containing aromatic heterocyclic group, for example, Naphthyl, 2-naphthyl, o-biphenyl and p-biphenyl. Specific examples of the oxidized triarylphosphine derivative which can be used in the present invention are shown in Tables 29 to 33 below. 319365 72 200806626 [Table 29] Compound Chemical structure 0〇 BP1 ό •ppo 0_9« EP3 ό EP4 OfVQ 〇=Η>Ό 73 319365 200806626 ~ [Table 30] EP6 0 _ ό EP6 0 One ό EP7 9 . - EP8 EP9 8+8 ό 74 319365 200806626 . [Table 31] ΕΡΙΟ cHiH} ΕΡ11 EP12 0 p Ο BP13 °0U° EP14. Qiu 75 319365 200806626 • [Table 32] EP15 p 63⁄4 EP16 ρ ό 〇 〇 EP17 ό 〇 EP18 0 〇 °=Γ〇^ι ^ Ου EP19 76 319365 200806626 * [Table 33] EP20 EP21 EP22 0 EP23 Op EP24. Off. ό 77 319365 200806626 Furthermore, a hole blocking material can be used in the hole blocking layer, which prevents (4) from reaching the electron injecting layer after passing through the light emitting layer, and can form a layer excellent in film formability. In the case of such a hole-blocking material, σ J Nissan (8-hydroxyquinolinic acid) (4-phenyl naphthol) aluminum or the like is complexed with a compound: a compound (double) (2-methyl I-ester acid) (4_Phenyl(10)) gallium and other graft complex compounds, or 2 q--Momo 7 - , mono-methane 4, 7-unit-based-1,1 fluorene (bcp) and other nitrogen-containing condensation Aromatic compound. The light-emitting layer is the same as the organic EL device of the present invention. Injection hole injection can be used to inject electrons through a cathode or electron injection layer through an anode or a hole injection layer when an external electric field is applied. The function of the electric field is to move the injected charge (electron). And electric power): providing a place where electrons and holes are recombined and making it light, but the ease of injection of holes and the ease of electron injection can be different, although expressed by the mobility of holes and electrons. The transport energy can be small and small, but it is better to move the charge of either side. The luminescent material of the organic EL it piece is mainly an organic compound, and the following compounds are used depending on the desired color tone. _糸

For example, 'the compound represented by the general formula [16] is suitable for obtaining the ultraviolet light to the violet light. U General formula [16] 319365 78 200806626 '〇r, (wherein 'X1 represents the following general formula [ (7) The group represented; χ2 represents any one of a phenyl group 1-naphthyl group and a 2-naphthyl group. The formula [17] is a parent (wherein 'm represents an integer of 2 to 5). "The phenyl group in X1 of the general formula [16] and the phenyl group, the phenyl group, the 2-naphthyl group represented by χ2 may also be subjected to one or more carbon numbers of from j to 4, and the carbon number is 1 to Substituting a substituent such as an alkoxy group, a thiol group, a fluorenyl group, a aryl group, an amine group, an dimethylamino group or a diphenylamino group, and when these substituents are plural, these groups may be mutually The ring is bonded to form a ring. Further, it is preferable that the U is not bonded to the phenyl group, and it is preferable to form a smooth vapor-deposited film because of good bonding property, and is represented by the above formula [16]. Specific examples of the compound may be as shown in the following formula (here, this represents a phenyl group). 319365 79 200806626

Among these compounds, in particular, p-quaterpheny 1 derivatives, p-quinquepheny 1 80 319365 200806626 • derivatives are preferred. In addition, in order to obtain the luminescence of the visible light region (especially blue to green), for example, a benzopyrene, a benzo-salt, a benzoxene, or the like may be used, and a metal chelate hydrazone may be used. A compound (styxin) compound or a styrylbenzene compound. Specific examples of such a compound include compounds disclosed in, for example, JP-A-59-! Other useful compounds are listed in ChemistiT Qf Coffee ^^·^ (1971) pp. 628-637 and 640. The metal chelated 8-hydroxyquinolinone compound can be used, and the compound disclosed in JP-A-63-295695 can be used. Representative examples thereof include an 8-hydroxyquinoline-based metal complex such as wheat (8-hydroxyquinoline) aluminum or a porphyrindione dilithium (dilithium®). Further, the above-mentioned styrylbenzene compound may be, for example, disclosed in the specification of the European Patent No. 031 9881 or the specification of the European Patent No. 373 582. Further, as disclosed in Japanese Laid-Open Patent Publication No. Hei-2-252793 The distyrylpyridinium derivative can also be used as a material for the light-emitting layer. Further, the polyphenyl compound disclosed in the specification of European Patent No. 0387715 can also be used as a material for the light-emitting layer. Fluorescent brightener, metal chelate 8 In addition to the quinone quinone compound and the phenethyl benzene compound, for example, 12-phthaloperynone (J-Appl) can also be used. · Phys., Vol. 27, L713 (1988)), 1,4-diphenyl-1,3-butadiene, 1,1,4,4-tetraphenyl-1,3-butadiene (The above is Appl· Phys· Lett·, 81 319365 200806626 / Volume 56, L799 (1 990) , a naphthoquinone imine derivative (JP-A-No. 2-305886), an anthracene derivative (Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. The oxadiazole derivative disclosed by Putian et al., the aldazine derivative (Japanese Patent Laid-Open No. 2-220393), and the pyrazoline derivative (Japanese Patent Laid-Open No. 2-22) 〇 394 )), a cyclopentadiene derivative (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2, 289, 891), and a styrylamine derivative (APP1. Phys. Lett) •, Volume 56, U99 (1 990)), coumarin compounds (Japanese Patent Laid-Open π gw%), International Patent Gazette W090/13148*Appl. phys. Vol. 58, 18, 1982 ( Polymer compound described in 1991), '9, 9 '10' 1〇-tetraphenyl-2, 2' _ hydrazine, ppv (poly(p-phenylene vinylene)) derivative, polyfluorene derivative or The copolymer of these compounds, etc., for example, has the following general formula [18] to general formula [2〇] Those structures, or 9,1〇_ bis (N- (4- (2- stupid group + vinyl) phenyl) _N_ phenylamino) provoke the like as the material for the light emitting layer general formula [18]

The site represents a monovalent aliphatic hydrocarbon group; nl represents (wherein RX1 and RX2 are each an integer of from 3 to 100, respectively). General formula [19] 319365 82 200806626

(wherein RX3 and rX4 n3 are each independently represented; the standing represents a monovalent aliphatic hydrocarbon group; and the clothes are not an integer of from 3 to 100). General formula [20]

And the R-knife independently represents a monovalent aliphatic hydrocarbon (wherein Μ each independently represents a hydrocarbon group; .. represents an integer from 3 to wo; Ph represents a phenyl group). As the luminescent material, a phenyl oxime derivative represented by the general formula [21] Uk formula [21] disclosed in Japanese Laid-Open Patent Publication No. Hei 8-12600 is used. [21] A1-L-A2 where 'A1 and A2 each independently represent a monophenylindenyl group or a diphenylephthene' and these groups may be the same divalent linking group). Μ is a different one; L represents a single bond or here, L-valent monocyclic or condensed or a mussel linking group represented by the general formula [23] of the general formula [23], which is a di & aromatic which may have a substituent A hydrocarbon group is preferred. In particular, the phenylhydrazine derivative represented by the following formula [22] is particularly suitable. 319365 83 200806626 (R21) r1

(wherein, IT and RZ4 respectively consider & calcination, -valent aromatic hydrocarbon group, hydrogenogen:, alkyl group, dilute group, cyclic monovalent aliphatic heterocyclic group, oxy group, diarylamino group, Also can be different. Η方曰^ quasi-ring base, these bases can be the same integer, · when Γ1^4# to 1"4 independently represent 0 or 1 to 5 RZ1 with each other, R, mutual: : Rf: The ground is 2, each can be the same, and each can also be different between the two sides, and between the two sides, RZ4 is different, and between RZ1 and 1^2 Between the two, a ring is formed to form a ring; L1 represents a single bond or may have a cyclic aromatic hydrocarbon group, and the substituent may have a substituent; the aromatic hydrocarbon group may be an intervening alkyl group, -〇-, -s- Or meal (in this case, RA shows alkyl or aryl)). General formula [23]

环基基'-valent aromatic hydrocarbon group, methoxy group, aryloxy group, diarylamine group: valency aliphatic heterocyclic group, -valent aromatic heterocyclic group, these groups may be the same 'may be different R5 and r6 each independently represent an integer of 319365 84 200806626 . When r5 and r6 are each independently an integer of 2 or more, rZ5 and R- are mutually identical, and each may be : identical, and RZ5 and RZ6 may be bonded to each other to form a ring representing a single bond or a divalent monocyclic or condensed cyclic aromatic group which may have a substituent / the divalent monocyclic ring which may have a substituent The cyclic aromatic smog group may be one in which the second group has a stretching group, 〇-, m (in this case, κ represents a burnt group or an aryl group). In the formula [23], it is suitably a phenylhydrazine derivative of the following formula [24] or not. General formula [24]

(wherein, Rzu to rZ3〇8, Rzu to RZ3G' adjacent groups may be connected to each other by an integer of 3). a cyclic ring group, - (iv) a fluorene atom, a silk, an alkenyl group, a -valent aliphatic heterocycloalkoxy group, an aryloxy group, a diarylamino group, or a different one; The base ' these groups may be the same junction to form a ring; kl represents c general formula [25] 319365 85 200806626

(wherein, RZ31 to RZ5. Octacycloalkyl, monovalent, and independently, independently represent a hydrogen atom, an alkyl group, an alkenyl group, a monovalent aliphatic, a heterogeneous, a shale, a diarylamine group. Or, may be different valence aromatic heterocyclic groups, these groups may be the same 1 U, and RZ31 pulls pZ5 〇 knot to form a ring; the _ 'adjacent groups can be connected to each other The table is not an integer from 0 to 3.) Phenyl onion two: Ϊ = 5. ] is represented by the general formula [26] as shown in the following general formula [26] ^

In the formula C, RZ51 $ RZ60 八刀 independently indicates gas 焉 + ρ I cycloalkyl, - valence # 辽 atoms, alkyl, alkenyl, 匕 香 香, alkoxy, aryloxy, two Aromatic amine monovalent aliphatic heterocyclic group, one group, or may be not (four). Gate: Ζ5 base, these groups can be the same J bureau not R, at the same time, RZ51 to RZ6. Linking to form 璟· Μ I — Λ 郯 郯 can be made into each other, k3 is not an integer of 3). A specific example compound of the above formula [26] or formula [27]. J" magical movements such as the following 319365 86 200806626

Further, the following compounds can also be given as specific examples.

Further, an amination compound represented by the following formula [27] can also be used as a light-emitting material. General formula [27] E1—(E\87 319365 200806626 (wherein h represents a valence, an integer from 丄 to 6; El represents an 11-valent aromatic hydrocarbon group; and E2 represents a compound selected from the group consisting of di- and aryl groups, An amino group of an amino group or an alkyl aryl group. Here, the parent structure of the n-valent aromatic hydrocarbon group represented by E1 is naphthalene, anthracene, 9-phenylanthracene, 9,1 fluorene-diphenyl. It is preferred that the base is a naphthacene, a perylene group, a biphenyl group, a binaphthyl group, a hydrazinyl group, and an amine group represented by E2 is preferably a diarylamine group. It is preferable to use 丨 to 4, and especially 2 is preferable. Among the general formula [27], an amine compound represented by the general formulae (10) to [3〇] is most suitable.

RV7 RV6 (wherein H Γ 8 independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aristocratic group, an aryloxy group, a valent aliphatic heterocyclic group, a -valent aromatic heterocyclic group, or Is an amine group selected from the group consisting of a di-amino group, a diaryl group, and a arylaryl group, at least one selected from the group consisting of a dialkylamino group, a diarylamino group, and an alkylaryl group. The amine group of the amine group; ... to Rys may be the same or 'different, and the adjacent groups may be bonded to each other to form a ring).

Ry11 Ry2〇 RV19

Ryi3 T y, Y^Ryi7 Ry14 know 15 is yie JL ^yie alkyl, dilute (wherein R R 2 2 independently represents hydrogen atom 319365 88 200806626 % alkyl, alkoxy, aryloxy, monovalent fat a heterocyclic group, a monovalent aromatic heterocyclic group, or an amine group selected from the group consisting of a dialkylamino group, a diarylamino group, and an alkylarylamine group, but within the range of ^" to Ry2, At least one of them is an amine group selected from the group consisting of a dih-heteroyl-arylamino group and a arylarylamine group; Ryi 1 to Ry2〇 may be the same 纟' or different, and the adjacent groups may be mutually Link to form a ring). General formula [30]

(wherein 'R~Ry34 are independently represented by a hydrogen atom, a pyridyl group, an alkenyl group, a % silk, an alkoxy group, an aryloxy group, a valent aliphatic heterocyclic group, a = a cyclic group, and a selected from the group consisting of two (four) Amino, diarylamine, alkylaryl & amyl' but within nRy34 'at least one is selected from dialkylamino, diarylamine, alkylarylamine The amine group of the group; ^ can be the same, or can be different from the m + "all, adjacent groups can be linked to each other to form a bad." General formula [31]

Ry37 Ry36 Ry3eO^Ry35 R-

Alkenyl group (wherein '52' independently represents a gas atom, a thiol 319365 89 200806626 • a cycloalkyl group, an alkoxy group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic aryl group, Or an amino group from a dialkylamino group, a diarylamino group, or a aryl group, but within Ry 5 to Ry52, at least one selected from the group consisting of a monoalkylamino group and a diaryl group The amine group of the amine group or the alkylaryl group; the groups F35 to 52 may be the same or different, and the adjacent groups may be bonded to each other to form a ring). General formula [32] *

Ry53 RyW Ry63 Ry62 R xb^Scb^Ry61

Ryse RV57 ^y58 |^y59 (wherein, Ry53 to Ry64 are from the 矣+ 7 knives respectively~ independently represent the atom, alkyl, alkenyl, cycloalkyl, alkoxy, dizzy I n. ^ a mussel aliphatic heterocyclic group, a monovalent aromatic fluorenyl heterocyclic group, or an amine group selected from the group consisting of a genus, a thiophene group, an alkyl aryl group, but Within f3 5 Ry64 & ^ , a ^ - to 1 ^ , at least one is an amine group selected from the group consisting of a diaminol group, a diarylamine group, and a arylarylamine group; Π Ry64 = the same Alternatively, different ones may be adjacent to each other. General formula [33]

(wherein, the cyclic alkyl group - independently represents a hydrogen atom, an alkyl group, an alkenyl group, a fluorenyl group, a fluorene heterocyclic group, a monovalent aromatic 319365 90 200806626. a heterocyclic group, or an optional An amine group of a arylamino group, a diarylamino group or a arylarylamine group, but at least one of them is selected from the group consisting of a dialkylalkylamino group and a diarylamine group. An alkyl group of an alkylarylamino group; R(6) to Rm may be the same or different, and adjacent groups may be bonded to each other to form a ring). General formula [34]

Ry7vv/Ry75 Ry^ RyB5

Ryny^~^Q^Ry84

Ry78H〇—C^y83

Ry79 Ry80 Ry81 ~^Rye2 (wherein R to R each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a % alkyl group, an alkoxy group, an aryloxy group, a monovalent aliphatic heterocyclic group, and a monovalent aromatic group. a 濉% group, or an amine group selected from the group consisting of a dialkylamino group, a diarylamino group, and an alkylarylamino group, but within 1 to 75, at least one selected from the group consisting of a dik-amino group The amino group of the monoarylamine group or the alkylarylamine group; the same to Ry86, or different, the adjacent groups may be bonded to each other to form a ring). General formula [35]

R' to Ry96 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkyl group, an alkoxy group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic hetero group, or a selected from An amine group of a dialkylamino group, a diarylamino group or an alkylarylamino group, but within Ry87 to Ry96, at least one selected from the group consisting of two 91 319 365 200806626. Alkyl female & aryl The amine group H 6 ^ of the amine group or the alkyl aryl group may be the same, and the adjacent groups may be bonded to each other. General formula [36]

(in the formula s, R to Ryll° independently represent a hydrogen atom, a deuterium group, an alkenyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, Or selected from the group consisting of a dialkylamino group, a diarylamine group, an alkylaryl group: a group: an amine group but within n Ryil, at least one selected from the group consisting of a dimercaptoamine group and a diarylamine The amino group of the alkylarylamino group, Ry97 to Ryll0 may be the same 'may be different, and the adjacent groups may be bonded to each other to form a ring). General Formula [37] RV^ RV118 RVt27 Ryi26

Ryiie^T\ Ry119 Ry12e Ryl2g

Ry114H^~Ry111 Ry12° I^-R Qing RY113 \y112 Ry12l\y122 (wherein R to R each independently represent a hydrogen atom, a deuterium group, a dilute group, a % alkyl group, an alkoxy group, an aryloxy group, a monovalent group An aliphatic heterocyclic group, a monovalent aromatic sulfenyl group, or an amine group selected from the group consisting of a dialkylamino group, a diarylamino group, and an alkylarylamino group, but within RY(1) to Rym, at least One is an amine group selected from the group consisting of 2 92 319365 200806626 - a mercaptoamine group, a diarylamine group, an alkylarylamine group; Ryl11 to Rym may be the same or different, and may be between adjacent groups. The interconnections are looped). The above-mentioned amine compound of the general formula [34] and the general formula [37] is more suitable for obtaining color-to-red light emission. Specific examples of the amine compound represented by the formula [] to the formula [37] described above include a compound having the following structure (only Ph represents a phenyl group).

319365 93 200806626

94 319365 200806626

Further, in the above formula [34] to the formula [37], a compound containing at least one styryl group represented by the following formula [38] or formula [39] in place of an amine group can be used (for example, containing European Patent No. 83 8 8 7 6 8 , 曰 特 特 。 3- 3- 3- 3- 3- 3- 3- 3- 3- 3- 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319 319

>y 129

(wherein, IT...5 nyl3l yV - to K represents independently a hydrogen atom, an alkyl group, a ring-based group, a -valent aromatic heterocyclic group; Π R_, an adjacent group: and a ring). %... general formula [39]

The work up to R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a monovalent aromatic heterocyclic group; and R"34 to Ryu8 each independently represent a hydrogen atom, a decyl group, and a mussel aromatic heterocycle. Or an amine group selected from the group consisting of a dialkylamino group, a diarylamino group, an alkylarylamine group, but within Rym to Ryl38, at least one selected from the group consisting of a dialkylamino group and a diaryl group An amine group of an amino group or an alkylarylamino group; Ryl32 to Ryl38, adjacent groups may be bonded to each other to form a ring). The above-mentioned at least one of the formula [38] or the formula [39] Specific examples of the styryl group-containing compound include compounds having the following structures (except, Ph represents a phenyl group). 319365 96 200806626

Ph

Ph

(H3C) 3C

〇(CH3)3

97 319365 200806626

98 319365 200806626

99 319365 200806626

(Rs-Q) 2~ai-〇-l3 (1 in 'L3 is a carbon atom number 6 to 0-L3 which is a phenolic ester (phen) 〇;l) work, bit early.Rq矣_ * Chuanji position, Q table does not 8-quinolinate ligand, Rs Table 4 will replace the 4 § 旨 好 好 好 好 好 好 好 好The 8-quinoline acid ester ring substituent which is stereoscopically blocked to k is exemplified by, for example, bis(2-methyl-8-indenyl-phenyl phenyl Win) and bis(2-f-based). n (4)) (p-phenylene (1-naphthoic acid) aluminum (III), etc. Further, it is possible to obtain a high-efficiency blue color by using doping according to JP-A-6-9953. A method of mixing green light. At this time, a host may be exemplified as the above-mentioned light-emitting material, and an X-dopant may be a strong fluorescent pigment such as blue to green, for example, with aroma 319365 100 200806626 It can be used as the same fluorescent pigment as the above-mentioned matrix. Specifically, as the substrate, there can be mentioned, for example, a diphenylethyl aryl-based bone (four) luminescent material: particularly preferably 4, 4,-bis (2, 2) - Phenylethylene)biphenyl '· can be used as a dopant such as diphenylaminoethyl bromide, particularly good example N, N-phenylaminoethphenyl. For white light emission The light-emitting layer is not particularly limited, but the following materials can be used, and the energy levels of the layers of the organic a-layered structure are defined, and the light is emitted by using the same note (European Patent No. G39G551) (Expression); the same as: (When the element is inserted into the channel and the white light-emitting element is described as an example (曰本特开平3_23〇5 layer (Japanese special Kaiping 2-22_#t carrier illuminating number bulletin) ); the luminescent layer is divided into a complex singular 2-nine material and formed (Japanese special Kai 4H hair 7 ^ different wavelength materials ( glory peaks 38G to 48 () η _ / / A report); Gamma-to-layer, and to make it two-body two-body (Jingguang Bofeng gift special Kaiping 6-mno bulletin) / light body and body (Japanese light body and green light layer contains red Rong == light layer contains blue The color firefly has a green phosphor and the area where the r element is removed, and the sub-energy contains: r, as a luminescent material, the object is applicable ( However, Ph stands for Stupid Base.) The well-known combination shown in τ 319365 101 200806626

102 319365 200806626

103 319365 200806626

104 319365 200806626 Η3〇〇

H3C NC h3co H3C0

H3c

H3C0 H3CO

H3C0 OCH3 003⁄4

Further, the light-emitting material of the present invention. It is possible to use a scalar metal atom in an organic electroluminescent device which can be used in an organic electroluminescence device, which can be a phosphorescent or doped material, usually a transition:: can be listed: such as an organometallic complex, The 6th cycle is better, the family is based on the 6th: to; the 5th cycle or the first 々々1 Λ k iron to the brother 1 1 is not good, and the 笫β from the brother 10 is not the best element aL is another 1 object. Specifically, it is ruthenium or platinum. In addition, the ligand is 2-phenyl t- or 2-(2,-benzo(tetra)yl), etc. Another 319365 105 200806626 is characterized in that the carbon atoms on these ligands are directly bonded to the metal. For example, p〇rphyri or a tetraazaline ring complex, wherein the central metal is a surface, etc., for example, it is suitable to use a permeation conjugate as shown below as a phosphorescent material ( However, ph stands for stupid base.)

319365 106 200806626

'+ The material used for the anode of the organic bismuth element can be used as a metal, alloy, or electric conductivity port which is used as a function (4) or more) or a mixture of substances as an electrode material. A specific example of such a negative electrode is exemplified by a metal such as Au or a material such as =. When forming this anode, it is possible to = = : = : the electrode is a thin film. In the case of increasing the luminescence of the anode, it is expected to be illuminating with respect to the anode, which is a characteristic of several hundred and two. Further, the sheet material of the anode is different, but it is a crucible. Moreover, the film thickness of the anode may be selected within a range of preferred, niD to 1 A m, and may be used at 10 to _nm for a cathode which can be used as a cathode of a wide element. Or the specific examples of gold (cut below), such as oxonium, oxonium alloy or these materials ❹~r, alloys, electrically conductive magnesium, lithium, magnesium, silver alloys, rare earth metals, and the like. This cathode can be exemplified by a specific example, and 乍 is an electrode material. Such an electrode material is, for example, a 'n-potassium alloy, vapor deposited or sprayed, &quot;,, rare earth, and the like. The cathode can be formed by a method in which 14 electrode materials are formed into a thin film to produce 319365 107 200806626 μ. When the light emitted from the light-emitting layer is taken out, the transmittance with respect to the 4-pole light emission may be greater than (10). The X' sheet resistance is from 100 Ω/□ or less, and * S is the cathode. The 1n S1 UM is L, and the film thickness is usually 1 〇 to 1 _, and preferably 50 to 2 〇〇 nm. . The material and method for the method for producing the organic EL element of the present invention form an anode, &amp;&amp; θ &amp;θ; the layer is required for the hole injection: the mouth is required to be the electron injection layer, and finally It is sufficient to form a cathode. The organic ruthenium can also be produced in the reverse order from the cathode to the anode. The organic EL element is fabricated on a calendered substrate. The substrate is a substrate supporting the organic EL element. The light is 4 〇〇 to 7 〇〇 m; : The transmittance of light in the first region is 5 〇 % or more, and it is better to use 9% or more. It is preferable to use a smooth substrate. Mechanical strength, (four degrees), and transparency, that is, no particular limitation '彳 For example, glass, synthetic resin sheets, etc.. For the glass substrate, for example, (4) glass, glass containing 钡•明, = glass, Mingshi A plate formed of an acid glass, a borax acid glass, a lock glass, and a quartz. Further, the synthetic resin plate may, for example, be a polycarbonate resin, an acrylic tree, or a polyethylene terephthalate. s resin, poly-sulfide (Poly Ether sulfide, PES) a plate of a resin, a polyfluorene resin, etc. The method for forming each layer of the organic germanium element of the present invention is a vacuum vaporization 1 beam irradiation, a sputtering, a light, ion-electric dry film formation method, or Wet film formation method such as spin coating, dip coating, flow coating (jet coating), inkjet method, or illuminating the illuminant on a donor film (d〇n〇r fnm) 319365 108 200806626; 2002-534782, 1 , sTLee, at al rocee lngs of SIDO2, P-784(2002)., l£ ^ ^ ^ ^ Γ TherffialIfflaglng,, „Lim;^ Applicable. The organic layer is particularly preferably a molecularly deposited film. The second one is: the bismuth refers to the deposition of a material compound in a gas phase state: open =: the solidification of the material compound in the solution state or the liquid phase state (knife-integrated), the difference in function which can be caused by agglomerated structure and high And distinguish it. Also in = 昭 57-51781, the public 瀚 ^ - ^ j in Japan 4 inch opening dissolved in the solvent and ... = the resin and other bonding agents and materials into a film, after the second I: When the thickness of the thin t film is too thick, in order to obtain a predetermined light output force, the electric = _ deteriorates, and conversely, the film T of each of the films (4) does not easily obtain sufficient illuminating brightness. Therefore, =: thickness is suitable for the __ range, but the dry circumference of 10 nm main U · 2 # m is better. In order to improve the stability with respect to the organic EL element, etc., a protective layer may be provided on the surface of the element, and the entire element may be covered or sealed. In particular, when the entire resin is a good or a double seal, the hardening property by the light is used == The current on the organic EL element of the invention, usually a direct current, a pulse current or an alternating current can be used. The current value, as long as it is 319365 109 200806626, is not particularly limited, but in consideration of the element, it is required to have as little electrical energy as possible, and it is possible to emit light with a power consumption or a life without destroying the component. The driving method (passive matrix) of the organic EL element of the present invention, and the broken matrix..) is also driven by an active matrix (active matriy method. Further, from the present invention) only from the anode The method of extracting light from the side is not the so-called bottom emission (bGtt(10)-n). The method of extracting light from the cathode side is called top emission (t〇p: 1SS1〇n). These methods or techniques are described in "Establishment of Everything, L" (published by the Japan Industrial Press in 2003). Further, the organic EL device of the present invention can also adopt a microcavity (mho (10) towel) structure. The organic rainbow element is a structure in which the light-emitting layer is held between the anodes of the anode disk, although the emitted light may cause interference between the anode and the cathode, but by reflecting the reflectance or transmittance of the anode and the cathode, etc. The optical characteristics, and the technique of secretly controlling the film thickness of the film at the time of the film, and actively utilizing the multi-interference effect, can control the wavelength of the light emitted from the element. Thereby, it is also possible to improve the chromaticity of the luminescence. The mechanism for this multi-interference effect has been described in AM-LCD Digest 〇f TechNical papers, 0D_2, p. 77_8〇 (2002) by J. Yamada et al. As described above, by using the organic EL element containing the σ-cain-amine compound of the present invention, long-term luminescence can be obtained with a low driving voltage. Therefore, the organic EL element can be used as a flat panel display such as a wall-mounted television or a variety of planar light-emitting bodies, and can be considered as a light source applied to a light source such as a copying machine or a printer, or a light source such as a 319365 110 200806626 liquid crystal display or a meter. ] Display panel identification lights, etc. Hereinafter, the present invention will be described by way of examples, but the present invention is limited to these examples. Also, the range of %^ indicating _ is not ~/〇 is not weight%. <Example 1> [Production of Compound (1)] The compound (1) (the compound represented by the compound of the following formula 3 (νπ)) was produced according to the synthesis scheme shown in the following Formulas 1 to 3. Formula 1

(III)

111 319365 200806626 • The following description will be made with reference to Equations 1 to 3. (1) Preparation of intermediate (111) In a nitrobenzene 10 g in a four-necked flask, N,N-diphenylamine 10 g, 4,4'-diiodobiphenyl 30 g, anhydrous carbonic acid were added. Potassium 9.4 g and steel powder ^ were heated and stirred at 200 ° C for 1 hour in a nitrogen gas stream. After the completion of the reaction, the reaction mixture was extracted with 100 g of benzene, and the toluene layer was concentrated. It was refined by a column chromatography using a silicone gel to obtain 8 g of a powder having a white color. It was confirmed to be the compound (III) by molecular weight analysis of FD-MS. . (2) Preparation of intermediate (VI) In a 1,3-didecyl-2-imidazolidinone in a four-necked flask, 3-bromo-9-phenylcarbazole (iv) 6e4g, aniline 2 was added. 3 g, anhydrous potassium carbonate 2· 〇g and copper powder 0.2 g were stirred and heated in a nitrogen gas stream at 20 (rc for 1 hr. After the reaction was completed, 1 g of hydrazine was extracted from the reaction mixture, and concentrated. A layer of a layer was obtained by purifying with a silica gel column chromatography to obtain 5 g of a white solid. It was confirmed by molecular weight analysis of Fd-MS that it was a chemical person (VI). The intermediate (111) obtained in the above (1) is 7·4 g, the intermediate (VI) obtained in the above (2) is 5.5 g, palladium acetate ruthenium 35 g, tri-tert-butyl and the Dioxane·5,-butanol sodium 2. 〇g was added to a 2-necked four-necked flask, 50 ml of dehydrated hydrazine was added thereto, and heated under reflux for 5 hours under a nitrogen stream. Into 5 ml of methanol, the precipitated solid was taken out by filtration, and then dried to give a compound (V11) of formula 3 (= compound (1)) 112 319365 200806626 μ crude product 9·2 g (yield 85%) The obtained crude product was purified by a silica gel column chromatography, and then subjected to sublimation purification. Elemental analysis of the compound (Model 24001 1 CHN0/0, manufactured by Perkin Elmer Co., Ltd.), 4-NMR, 13C- NMR (manufactured by JEOL Ltd., GSX-270W) was confirmed to be the compound (1). The following is the result of elemental analysis of the product, and the 1H-NMR spectrum of the obtained compound (1) is shown in Fig. 1. Result· Calculated value (%) as C48H35N3 : C : 88· 18 Η : 5· 40 N : 6· 43 Measured value (%) : C : 88· 21 Η ·· 5. 38 Ν : 6· 41 Still, The 3-bromo-9-phenylcarbazole (IV) used in the manufacture of the compound (1) is the method described in the Journal of Industrial Chemistry, published in 1967, Vol. 7, pp. 63, using carbazole. After the bromination at the third position, the iodinated benzene is reacted by a U11 mann method using a copper catalyst. <Example 2> [Production of Compound (2)] According to Formula 4 below The compound (2) (the compound represented by the compound (X) in the following formula 5) is produced by the synthesis scheme shown in Formula 5.

319365 113 200806626

One side explained. In the following, the preparation of the intermediate (IX) of the formula 4 to the formula (1) is carried out in a four-necked flask, and 10 g of the ruthenium ruthenium is added, and a phenyl hydrazine (3 gg, Anhydrous carbonic acid unloading 9.4g and (iv) /.^ in a randomized milk stream at 200t heating (4) l (M, hour. After the end of the reaction 'take 1% of the formazan and luug of the reaction mixture from the reaction mixture, and The toluene layer was concentrated, and purified by using a JS k jU ^ noisy 7 S column chromatograph of Shishijiao to obtain a powder having a pale yellow fluorescent color of 9 g. Funeral A pri-Me Μ , Tian Jun by FD MS The molecular 1 analysis confirmed that it was a compound Π) Π. (2) Production of Compound (2) 7.9 g of the intermediate (IX) obtained in the above (1), and the intermediate prepared in the above Example (2) ( VI) 5 5g, palladium acetate ruthenium 35g, tri-tert-butylate 1.34g and sodium terp-butoxide 2 〇g were added to a 2〇〇ml four-necked flask and dehydrated xylene 5〇ml was added thereto in a nitrogen gas stream. The reaction was poured into methanol 5 〇〇mi, and the precipitated solid was removed by filtration, and then dried under vacuum to obtain a chemical in the formula 5. The crude product of the product (χ) (== compound (2)) & ig (yield 72%). The obtained crude product (4) was refined by a ruthenium column chromatography, and the sublimation purification was carried out. Elemental analysis of this compound (manufactured by Perkin Elmer Co., Ltd., 24 〇〇 ι 319365 114 200806626 CHN0/0 type), NMR, 13C-NMR (manufactured by JEOL Ltd., gsx-270W) was confirmed to be the compound (2). As a result of elemental analysis of the product, the 1H and MR spectra of the obtained compound (2) are shown in Fig. 2. Elemental analysis results as C52H37N3 Calculated value: C: 88.73 η : 5.3〇N : 5. 97 Measured value ( %) : C: 88.56 H: 5.38 N: 6.03 <Example 3> [Production of Compound (3)] Compound (3) was produced according to the following synthesis schemes shown in Formula 6 to Formula 7 (in the following Formula 7) a compound represented by the compound (XIII).

The following description will be made with reference to Equations 6 to 7. (1) Preparation of intermediate (XII) In a four-necked flask, ruthenium, 3-dimethyl-2~-imidazolidinone 1 〇g was added, 115 319365 200806626 'into 3-bromo-9-phenyl material (10) 6 .4g, Bucaoamine core, anhydrous potassium carbonate 2. 0g and copper powder 〇. 2g, heated in a nitrogen gas stream at 2 〇〇t: heating 〇 〇 hours. After the completion of the reaction, extraction was carried out from the reaction mixture with 1 g of toluene, and the toluene layer was concentrated. 6 g of a white solid was obtained by subjecting a time-column column chromatography to purification. From the molecular weight analysis of FD_MS, it was confirmed that the compound (XII). (2) Production of Compound (3) 7.4 g of the intermediate (ln) obtained in (1) of Example 1 and 6.0 g of the intermediate (XII) obtained in the above (1), acetic acid Palladium ruthenium 35 g, tri-tert-butylphosphine 1.34 g, and sodium terp-butoxide 2.0 g were placed in a 2-inch flask of 4 ml and 50 ml of dehydrated xylene was added thereto, and the mixture was heated under reflux for 1.5 hours under a nitrogen gas stream. . The reaction solution was poured into 5 〇〇ml of decyl alcohol, and the precipitated solid was taken out by filtration and then dried under vacuum. The crude product of the compound of formula 7 (χιιι) (chemical substance (3)) was obtained in 7 g (yield: 65%). The obtained crude product was purified by an Escherichia coli column chromatography, followed by sublimation purification. It was confirmed by elemental analysis (manufactured by PerkinElmer Co., Ltd., 24〇〇11 CHN0/0 type) NMR, %-NMR (manufactured by JEOL Ltd., gSX-27 〇w) to confirm that it was the compound (3). The following is the result of elemental analysis of the product. Elemental analysis result: Calculated value (%) as c53h38n3 : C : 88· 80 Η ·· 5· 34 N : 5· 86 Measured value (%) : C ·· 88· 61 Η : 5. 38 Ν : 6. 01 <Example 4> [Production of Compound (4)] Compound (4) 116 319365 200806626 - (Compound 8 represented by the compound (XIV) in the following formula 8) was produced according to the synthesis scheme shown in the following formula 8

Production of Compound (4) The intermediate (Ιχ) 7·%, intermediate = (ΧΙΙ) 6·Og, palladium acetate ruthenium 35 g, and tri-tert-butylphosphine prepared in (1) of Example 2 only are described monthly. h 34 g and tert-butanol, 2.0 g were placed in a 200 ml four-necked flask, and 5 ml of dehydrated toluene was added thereto, and heated under reflux for 5 hours under a nitrogen gas stream. The reaction solution was poured into 5 GGml of f-alcohol, and the precipitated solid was taken out, and then dried under vacuum. The crude product of the compound (χιν) (= compound (4)) of the formula 8 was obtained in an amount of 8.5 g (yield: 71%). The obtained crude product was purified by a silica gel column chromatography, followed by sublimation purification. This was confirmed to be the compound (4) by elemental analysis of the compound (manufactured by Perkin Elmer Co., Ltd., 2400 Π CHN0/0 type), H-NMR, and 13C-NMR (manufactured by JEOL Ltd., gsx-270W). The following is the result of elemental analysis of the product. Elemental analysis result. Calculated value (%) as C56H39N3 ·········································· <Example 5 &gt; [Production of Compound (5)] 117 319365 200806626 h • The oxime (5) was produced according to the synthesis scheme shown in the following Formulas 9 to 11 (the compound (XIX) in the following Formula 11 is represented) compound of). Equation 9

(XVIII)

The following description will be made with reference to Equations 9 to 11. (1) Production of intermediate (XVI) Amine In a nitrobenzene coffee in a flask, N,N-bis(p-biphenyl 0 8 g, 4'4 io-iodobiphenyl 30 g, Anhydrous potassium carbonate 9.4g and steel powder. §, stirred in a nitrogen gas stream at 2 Torr (rc heating for 1 hr. After the end of the reaction 319365 118 200806626, from the reaction mixture with 100 g of benzene which 4 &quot; Take and concentrate the layer. Purify by using the column chromatography of Shixia, 9 g of yellow fluorescent powder. The molecule a of FD-MS has a light compound. 'Confirming that it is (2) Preparation of intermediate (XVIII) In a 1,3-didecyl L 唆嗣i〇g in a four-necked flask, 3-y-9-phenyl M(IV) 6.4 was added. g, 4-aminobiphenyl 4 2g, anhydrous carbonic acid unloaded 2.0g and copper powder 0.2g, in a nitrogen gas stream with 2 〇 generation _ fell for 10 hours. After the end of the reaction, with 1 () () g of A The extract was stupid, and the toluene layer was concentrated. A white solid (10) was obtained by using a column chromatography of Shiqi gum. The molecular weight analysis by FD-MS confirmed (XVIII). &quot; (3) Compound (5) Manufacture of the above (1) Intermediate (XVI) 9·6g, intermediate 〇^111) prepared in the above (2) 6.62, palladium acetate 0.35 §, tri-tert-butylphosphine 1.34g and sodium second butoxide 2· 〇g 2 ml of a four-necked flask was placed, and 50 ml of dehydrated xylene was added thereto, and the mixture was heated under reflux with a nitrogen gas stream to reflux for 5 hours. The reaction solution was poured into methanol 5 〇〇m 1 , and the precipitated solid was taken out by filtration. Thereafter, it was subjected to hot vacuum drying to obtain a crude product of the compound (χιχ) (= compound (5)) of the formula n (7.8 g (yield: 62%). The obtained crude product was obtained by a silica gel column chromatography. After the product was purified, sublimation purification was carried out. The alizarin analysis of the compound (manufactured by Perkin £1mer, 24001 1 CHN0/〇 type), 泔-NMR, 13C-]\iMR (made by JEOL, gsx-) 270W) Analysis confirmed that it is compound (5). The following is the result of elemental analysis of the product. 119 319365 200806626 % - Results of analysis of all factors · Calculated value (%) as C6U3 : c : 89· 60 Η : 5. 72 N: 4. 68 Measured value (%): C: 89·50 Η : 5·48 Ν : 5·〇2 <Example 6> [Production of Compound (6)] According to the following Formula 12 and Synthesis flow shown is manufactured of 13 people (6) (in the formula 13 compound (XXIII) represents a compound) &quot; Formula 12

Hereinafter, the description will be made with reference to Expressions 12 to 13. (1) Production of Intermediate (XXI) In a nitro group of a four-necked flask, ruthenium-phenyl-indole-(p-biphenylyl)amine 15 g, 4, 4,-diiodo linkage was added. 30 g of benzene, 9.4 g of anhydrous potassium carbonate, and 0.8 g of copper powder were heated and stirred at 2 ° C for 1 hour under a nitrogen gas stream. Reaction 319365 120 200806626 After the end, extraction was carried out with a lGGg of toluene, and the toluene layer was concentrated. Purification was carried out by using a column chromatography of Shixia gum to obtain 10 g of light granules = powder. By FD-MS, the molecule is eight cylinders ^ Zhongxian (χχι). In the knives, it was confirmed that it was the compound (2). The production of the compound (6) was obtained by the above-mentioned (1) (3), 83 g of the intermediate (XVIII) obtained in the above (2), and acetic acid. 〇.35g, tributylphosphine 1.34g and sodium t-butoxide 2〇g were added to a 4 〇〇mi four port and a dehydrated M5Qm was added thereto to reflux under a nitrogen gas flow for 1.5 hours. The liquid was poured into 5 〇〇ml of decyl alcohol, and the solid which was taken out by hydrazine was dried under vacuum, and the crude product of the compound (XXIIJ) (= compound (8)) in the formula 13 was obtained (yield (4)). The obtained crude product was purified by a silica gel column chromatography, and then subjected to sublimation purification. Elemental analysis of the compound (manufactured by Perkin E. Co., Ltd., model 2400II CHN0/0), lH_NMR, and 13c_NMR (manufactured by Nippon Electronics Co., Ltd., GSX 27GW) Analysis 'confirmed as compound (6). The following is the result of elemental analysis of the product. Elemental analysis result: Calculated value (%) as C6()H43N3 : c : 89·41 Η : 5. 38 Ν : 5. 21 Measured value (%): C ·· 89· 25 Η ·· 5· 35 Ν : 6. 40 <Example 7> [Product of compound (7) (Compound of the formula 15 (χχνί))] is synthesized according to the flow shown in Formula 14 to Formula 15 below is produced compound (7). 319 365 121 200 806 626 'Formula 14

α) Preparation of intermediate (xxv) In 10 g of nitrobenzene in a four-necked flask, Ν-phenyl, _(9-phenanthryl)amine 20 g, 4,4,-diphenylbiphenyl 3 〇g, Anhydrous carbonic acid was decomposed and known as copper powder. 8 g' was extracted under a gas stream at 2 Torr (heating with rc, at the end of the reaction.) After extraction, 1 g of toluene was extracted from the reaction mixture, and the toluene layer was concentrated. The product was purified by using a column chromatography of Shiqi gum to obtain 12 g of a powder having a pale yellow camping light. By molecular weight analysis of FD-MS, it was confirmed that it was a compound (XXV). ', (2) Compound ( 7) The intermediate (xxv) obtained in the above (1) is 8.7 g, the intermediate (VI) obtained in the above (2) is 6 6 g, the wrong (tetra) 35 g, and the tri-t-butyl lin 1 · 3 4 g and the second _ &amp; amp η, one to the nano 2 2. 〇 g added to the 200 ml four-necked flask

Medium, and add 50 ml of dehydrated dimethyl I T, and add it back under nitrogen gas flow 319365 122 200806626

II CHN0/0 type), ιΗ-面, 13 νττ alcohol 50〇m 1 , filtered and taken out for drying. The compound (χχνι) in the formula 15 was obtained in an amount of 8·5 g (yield: 63%). After purification by a rubber hose, it is subjected to sublimation analysis (manufactured by Perkin Elmer, 2400 C-NMR (GSX-270W, manufactured by JEOL Ltd.), and refined by wind. 4 Elemental analysis of this compound (Perkin's analysis) The compound (7) is the compound (7). The following is the result of the analysis of the product, and the lH-NMR spectrum of the compound (7) is shown in Fig. 3. The result of the analysis of the 70-factor analysis: calculated as C56H39N3 (%) ·· c : 89· 21 Η ·· 5· 21 N : 5· 57 Measured value (%) : C : 89· 31 Η : 5. 38 Ν : 5. 31 <Example 8 &gt; [Production of Compound (8)] According to the following formula The compound (8) (the compound represented by the compound (XXX) in the following formula 17) is produced by the synthesis scheme shown in the 16th to the 17th formula.

Equation 17 123 319365 200806626

Hereinafter, the description will be made with reference to the expressions 16 to 17. (1) Preparation of intermediate (XXVIII) In a succinylbenzene 1 〇g in a four-necked flask, N-(1-naphthyl)-N-(2-naphthyl)amine 18 §, 4, 4'- Diiodobiphenyl 3 (^, anhydrous potassium carbonate 9.42 and copper powder 0. 8g, heated and stirred at 200 ° C for 1 hour under a nitrogen stream. After the reaction is completed, from the reaction mixture with l〇〇g of the stupid Extracting and concentrating the ruthenium layer, and purifying by using a column chromatography of Shiqi gum to obtain 10 g of powder having pale yellow fluorescence. It was confirmed to be a compound (XXVIII by molecular weight analysis of FD-Ms; (2) The intermediate (XXIX) was produced by substituting 2-naphthylamine for the indole-naphthylamine of (1) of Example 3, and carrying out the method described in Example 3 (1). In the same manner, the intermediate (XXIX) was produced. (3) Preparation of the compound (8) 8.7 g of the intermediate (mm) obtained in the above (1), and 6.2 g of the intervening body uXIX obtained in the above (2), cool Acid u.35g, tri-tert-butyl scale 1.34g and di-n-butanol steel 2〇g plus 2〇〇mi four-necked flask, and add dehydrated dimethyl! ^ηι &gt; T 50 m1, heated under reflux with a nitrogen stream of 1.5% by volume. The reaction solution was poured into 5 〇〇ml of 曱醢 , ,, and the precipitated solid was removed by filtration. 319365 124 200806626 • Thereafter, it was dried under vacuum. The crude product of the compound (χχχ) (= compound (8)) of the formula 17 was obtained in an amount of 7.8 g (yield: 6 %). The obtained crude product was purified by a Shi Xizhu column chromatography, and then subjected to sublimation purification. The compound (8) was confirmed by elemental analysis of the compound (manufactured by Perkin Elmer Co., Ltd., c-type )), MMR, 13C-NMR (manufactured by JEOL Ltd., GSX-27h). The following is the result of elemental analysis of the product. Elemental analysis result: Calculated value (%) as c6()H4lN3 : C : 89. 63 Η : 5. 14 N : 5. 23 measured value (% ) ·· C ·· 8 9 · 5 0 Η ·· 5 2 3 Ν : 5 · 2 7 <Example 9 &gt; [Production of Compound (9)] The compound (9) was produced according to the synthesis scheme shown in the following Formula 18 (the compound (χχχπ) in the following Formula 18) compound of). Equation 18

(1) The intermediate (XXXI) was produced by using fluorenyl-phenyl-indole-(2-naphthyl)amine instead of the fluorenyl-phenyl,-(p-naphthyl)amine of (1) of Example 2, and The method described in (1) of Example 2 was carried out in the same manner to produce an intermediate (XXXI). (2) Production of Compound (9) 319365 125 200806626, the foregoing Example 8

(XXX 11) (= Compound (9)) crude product 78g (yield: 65%). An intermediate (XXIX) 6 lg obtained by cutting 7.9 g of the intermediate (xxxi) obtained in the above (1), butyl dibutylphosphine acetate 1 · 31⁄2, and rutin 破 〇 〇 a _ - The 粗Is column chromatography was used to purify the obtained crude product, and then sublimation was carried out by elemental analysis of the compound (manufactured by PerkinEimer Co., Ltd., Model 2400II CHN0/0), 沱-NMR, 13C-NMR ( It was analyzed by Nippon Electronics Co., Ltd., GSX-270W, and it was confirmed to be a compound (9). The following is the result of the elemental analysis of the product. Elemental analysis result: Calculated value (%) as c56h39n3 ·· C ·· 89· 21 Η : 5· 21 N ·· 5. 57 Measured value (%) : C : 89. 02 Η : 5. 38 Ν : 5· [Example 1 〇&gt; [Production of Compound (10)] The compound (10) (a compound represented by the compound (XXXV) in the following formula 19) can be produced according to the synthesis scheme shown in the following formula 19. Equation 19 126 319365 200806626

(1) The intermediate (XXXIII) of the intermediate (XXXIII) is the same as the intermediate (xxv) obtained by the method described in the above (1), and the intermediate (χχχι) 11(TM) was produced by the method described in (1) of Example 7 (method of Formula 14). (2) The intermediate (XXXIV) was produced by using 9-phenanthrylamine instead of the above Example 3. (丨) 1-naphthylamine in the method (method of Formula 6) described in the same manner as in the method (Formula 6 of Example 6) of Example 3, to produce an intermediate (χχχιν) (3) Preparation of Compound (1〇) The intermediate (ΧΧΧΠΙ) obtained in the above (1) is 8·7 g, and the intermediate obtained in the above (2) is further (17). Palladium acetate 035 §, tri-tert-butylphosphine 1.34 g and sodium terbutyrate 2.0 g were placed in a 2-inch flask of 4 〇〇ml, and 50 ml of dehydrated diphenylbenzene was added thereto, and heated under reflux under a nitrogen gas stream. The reaction solution was poured into 500 ml of decyl alcohol, and the precipitated solid was taken out by filtration, and then dried under vacuum to give a compound of formula 19 (χχχν) (=5 (10) () Crude product 8, 2 g (yield 60%). The obtained crude product was purified by a silica gel column chromatography, followed by sublimation purification. Elemental analysis by this compound (Perkin Elmer &amp; System, 24〇〇ιι 319365 127 200806626 CHNO/O type),] h-NMR, 13C-NMR [曰士币&amp;., MK (made by JEOL Ltd., GSX-270W) analysis, Cui 5 is a compound (J 〇). The following results, ^ is not the elemental analysis element analysis result of the product: as Ν: 4. 92 Ν : 4. 67 Calculated value (%) ·· c : 90. 01 Η : 5. 07 Measured Value (%): C: 90·20 η : 5 13 <Example 11> - [Production of Compound (11)] "The compound (1) was produced according to the synthesis scheme of the formula::) Compound (χχχνπι)

Equation 20 Cut J

(1) The intermediate (XXXVI) is produced by using the amine in the method (formula: method) described in the N-phenyl-N-(indol-9-yl)amine: and as described in the above (1) Method (The same operation as in Formula 14 is carried out to produce Intermediate (XXXVI).) (2) Preparation of Intermediate (xxxvii) Using 9-mercaptoamine in place of the above-described method (the method of Formula 6) The method described in (1) of 3, and the same procedure as in the method of (Third method (XXXVII) of Formula 6) of the method described in Example 3 (1), (3), to produce the compound of the intermediate (3) ( Production of 11) The intermediate (χχχνι) obtained in (1) is 8. 7 g, the intermediate um (1) 7. Gg obtained in the above (2), acetic acid u. 35 g, and tri-tert-butylphosphine g And the younger-butanol 2· 〇g was added to a four-necked flask of 2〇〇mi, and dehydrated-toluene 50m was added to the second. The mixture was heated under reflux with a nitrogen gas stream to reflux 1. 5 small ^ The reaction solution was poured into methanol 50 〇 In ml, the precipitated solid was taken out by filtration, and then γ was dried under vacuum. The crude product of the compound (xxxvm) (=r compound (11)) in the formula 2 was obtained in an amount of 8.3 g (yield: 62%). The obtained crude product was purified by a silica gel column chromatography, and then subjected to sublimation purification. It was confirmed by elemental analysis (manufactured by Perkin Eimer Co., Ltd., model 24001 1 CHN0/0), 沱-NMR, and 13C-NMR (manufactured by JEOL Ltd., GSX-270W) to confirm the compound (11). The results of the elemental analysis of the product are shown below. Element is the result of analysis · Calculated value (%) as C64H43N3 : C : 90· 01 Η : 5· 07 N : 4. 92 Measured value (%): C: 90.12 Η: 5.18 70 <Example 12 &gt; [Compound ( (Production of 12) The compound (12) (the compound represented by the compound (XLI) in the following formula 21) is produced according to the synthesis scheme shown in the following formula 21. Equation 21 129 319365 200806626

The method described in the method U! of the method described in the above-mentioned Example 1 (1) is used in place of the oxime, fluorene-diphenylamine of the formula: Body (XXXIX). The method of the same procedure is carried out to produce (2) the production of the intermediate (XL) _.r. / aniline, and the enthalpy of the first embodiment (1) and the second butyl (tetra) G.35g, three 5小时。 The third butyl phosphine was added to the nitrogen gas stream under reflux. The methanol was added to 5 ° 〇mi, and the precipitated solid was taken out by filtration, and then the compound in the formula 21 was coarsely grown (the crude product of the method was obtained by the method of column chromatography). After the sublimation purification, the compound was analyzed by a knife (Perkln Elm Co., Ltd., 2400 Π CHN0/() type), 319365 130 200806626 H-NMR, C-NMR (Japan Electronics, gsx-270W) analysis. The result of elemental analysis of the product is shown below. The result of the elemental analysis is as follows: c5()H39N3 Calculated value (%) ·· C ·· 88. 07 Η : 5. 77 N : 6 16 Measured value (%)·· C: δ8·21 Η: 5.81 Ν: 5.98 <Example 13 &gt; [Production of Compound (13)] The compound (13) was produced according to the synthesis scheme shown in the following formula 22. (Compound represented by the compound (xuv) in the following formula 22).

(1) Production of Intermediate (XLII) N-(4iphenyl)-N-phenylamine is used in place of N, N-di in the method (method of Formula i) described in the above Example (1) Phenylamine, and the method described in (1) of Example 1 (method of Formula 1) were subjected to the same operation to produce an intermediate (XLII). (2) Production of Intermediate (XLIII) The use of 4-fluoroaniline in place of the aniline in the method of the method (2) described in the above Example (2), and the formula described in (2) of the Example (2) Method 2) The same procedure was carried out to produce an intermediate (xu(1). 319365 131 200806626 (3) Production of Compound (13) The intermediate (xLn) 7.k obtained in the above (1), intermediate prepared in the above (2) ^ xmI) 5.6g, acetic acid|G〇.35g, tri-tert-butylphosphine 1.34g and butanol sodium 2. Gg is added to a 2 GGml four π flask, and dehydrated xylene _ is added thereto. The reflux was heated under a nitrogen stream for 5 hours. The reaction solution was poured into methanol H, and the precipitated solid was filtered, and then dried under vacuum. The crude product of the compound (xliv) (=k compound (13)) in the formula 22 was obtained in an amount of 7. g (yield: 64%). The obtained crude product was purified by a rubber tube column analyzer, and then subjected to sublimation purification. It was confirmed by elemental analysis (manufactured by Perkin Elmer Co., Ltd., CHN0/0 type), 沱-NMR, and 13C-NMR (manufactured by JEOL Ltd., GSX-270W) to confirm the compound (13). The following is the result of the elemental analysis of the product. The element is the result of the analysis. The calculated value (%) as C48H33 F2N3: C: 83· 58 H: 4· 82 F: 5. 51 N: 6. 09 measured value (%) : C ·· 83. 63 Η ······································ Compound (14) (a compound represented by the compound (XL V11) in the following formula 23). 23 132 319365 200806626 h3cov

The method described in (1) of N-(4-decyloxyphenyl)~1 is used (H in the formula i is described by way of example and the method described in (1) of the first embodiment (work 2:= : Diphenylamine, as, manufacturing intermediate (XLV). / / Performing the same operation (2) Production of intermediate (XLVI) Using 4 曱 milk base amine instead of the method of the foregoing example (method of formula 2) The method of the above-mentioned "5" method (the method of the formula 2) is carried out as follows: (1) (8) The production of the compound (10) is described as the "manufacturing intermediate", and the (four) is obtained in the above (1). Body (XLV) 1th, (4)-free, tri-tert-butylphosphine 1: 2nd yano-nanophthalate 2.0g added 200ffll of four-burning spectacles, and it is added to the benzene to 5 〇ml The mixture was heated to reflux for 1.5 hours under a nitrogen gas stream, poured into a T-coal 5 coffee, and the precipitated solid was taken out by filtration, and then m was dried to dryness to obtain a compound (10) (1) compound of formula 23: 6. 9g (yield 6 %%). The product obtained by (4) column chromatography:: the crude product is refined, and then sublimed and refined. The analysis of the bismuth (perkin Elmer, 24 〇〇) π(3) age / 31 9365 133 200806626 〇, NMR, 13C-NMR (Gsx to 270W, manufactured by JEOL Ltd.) was confirmed to be the compound (14). The results of elemental analysis of the product are shown below. Elemental analysis results··as c5〇 H39n3〇2 Calculated value (%) ·· C ·· 84· 12 Η ·· 5· 51 N ·· 5· 89 Measured value (%) ·· C ·· 84. 18 Η : 5. 42 Ν : 5. <Example 15> [Production of Compound (15)] The compound (丨5) (the compound represented by the compound (L) in the following formula 24) is produced according to the synthesis scheme shown in the following formula 24).

(1) Production of Intermediate (XLVIII) Using Ν-(4-pyridyl)-fluorene-phenylamine in place of N in the method (method of Formula 1) described in the above-mentioned Example (1) N-diphenylamine, and only the method described in (1) of Example 1 (the method in the formula) was subjected to the same procedure to produce an intermediate (XLVIII). The production of the wood (2) intermediate (XLIX) is carried out by substituting the 4-amino group for the aniline in the method (the method of the formula 2) described in the above (1), and with the example i The process described in (2) (the method of Formula 2) was carried out in the same manner to produce an intermediate (XLIX). 319365 134 200806626 (3) Preparation of Compound (15) The intermediate ULVIII) prepared in (1) is 7. 2g, the middle (»ux) of the above (2) = 5.4g, acetic acid (tetra), 35g, three_third Butylphosphine 1.342 and tert-butanol fine 9 〇丄 2 2.0 g were added to a 200-m four-necked flask, and 50 ml of dehydrated dimethyl sulphate was added thereto, and heated under a nitrogen stream to reflux 1.5 liters. The word reaction was poured into the formazan to 5 〇〇mi +, and the precipitated solid was removed by filtration and then allowed to dry under vacuum. The crude product of the compound (1) and the compound (15)) in the formula 24 was obtained in a yield of 6·5 g (yield: 62%). The crude product thus obtained was purified by a Shixi rubber column chromatography, and then subjected to sublimation purification. It was confirmed by elemental analysis (manufactured by Perkin Eimer Co., Ltd., 24(10)H C{JN〇/〇 type), H-NMR, 13c-NMR (made by JEOL Ltd., gsx-270W) to confirm that it was a compound (15). . The results of the elemental analysis of the product are shown below. Elemental analysis result: Calculated value of C46H33N5 (%)·· c : 84.25 Η : 5. 07 Ν : 10. 68 Measured value (%) : C : 84· 21 Η : 5· 18 Ν : 10. 61 〈Implementation Example 16 &gt; [Production of Compound (16)] The compound (16) (the compound represented by the compound (LI II) in the following formula 25) was produced according to the following synthetic scheme of the formula (25). 25 135 319365 200806626

(1) Manufacture of the intermediate (LI) (1) The succinylamine (IV) Substituent Example The method described in the method (the method in the formula 1) is described in (1) Method (for the formula η; and for the preparation of the intermediate αι).仃 The same operation (2) Preparation of intermediate αιι) 2-amino group was used. The method of the present invention (UI) is carried out in the same manner as in the production of the compound (10) of the compound (3) described in (7) of the present invention, in the same manner as in the preparation of the compound (10). The obtained intermediate (U) 7.2 g, the aforementioned state and third butanol/J/Japanese acid 1 bar, tri-tert-butylphosphine h34g into a dehydrated dimethyl-. 200mi four-necked flask, and Add 5 〇ml, heat under nitrogen gas to reflux for 1.5 hours. Pour the reaction solution into the formazan nn 7 1 ^ The hot vacuum dry roasting = filter out the precipitated solids, then make n U,,, To the compound (LIII) in the formula 25 (=the compound will be the product, the product 6·8 § (yield 63%). After the product is refined by the Shixi rubber column chromatography servant 八#, the product is refined. Sublimation and refining. It was confirmed by analysis of this product, which was made by Perkin Elmer (2400II CHN0/136 319365 200806626 • 〇 type), j-NMR, 13C-NMR (Gbx-270W). Compound (16). The results of elemental analysis of the product are shown below. Elemental analysis results: As C44H31N3S2, the difference value (%): c: 79.37 H: 4.69 NU1 S: 9. 63 C: 79.40 Η: 4·65 Ν: 6·25 S: 9.70 <Example 17> [Production of Compound (17)] Compound (17) was produced according to the synthesis scheme shown in the following Formula 26 (see below) a compound represented by the compound oyster in Formula 26).

3 Guang-9-(4-methylphenyl) σ Kawa is used instead of the method described in the above Example () (3 in the method of Formula 2). The same procedure as in the method (2 in the formula 2) described in the example (2) was carried out to produce an intermediate (LIV). (2) Production of Compound (17): The intermediate (1(1) 7々, the intermediate (LIV) obtained in the previous example, 5.5 g, the wrong acid μ: butylphosphine 1 and the third Ding Axis Addition (10) — 319365 137 200806626 • Add 5 ml of dehydrated xylene to the mixture and heat to reflux for 1.5 hours under a stream of nitrogen. Pour the reaction into 5 mL of methanol and filter out. After the precipitated solid was dried under vacuum, the crude product of the compound (LV) (= compound (17)) of the formula 26 was obtained (yield: 82%). The obtained crude product was purified, and then subjected to sublimation and fine coating. Elemental analysis of the compound (manufactured by Perkin Elmer Co., Ltd., 2400 Π CHN0/0 type), NMR, 13 〇 R (made by JEOL Ltd., GSX-) 270W) Analysis and confirming that it is compound (17). The following is the result of elemental analysis of the product. Elemental analysis result·· Calculated value (%) as C49H37N3 : C : 88. 12 Η : 5. 58 N : 6. 29 Measured value (%) : C : 88 · 09 Η : 5. 38 Ν : 6. 53 &lt;Example 18&gt; [Production of Compound (18)] According to the following formula Compound (18) (a compound represented by the compound (LVII) in the following formula 27) is produced by the synthetic scheme shown in 27.

Method for using 3-bromo-9-(4-fluorophenyl)carbazole in place of 3-bromo-9-phenylcarbazole in the method of 138 319365 200806626 of the above Example 1 (method of formula 2) The method (2) and the operation described in (2) of Example 1 are carried out to produce the intermediate (LVI). (2) Production of Compound (18) The foregoing examples are carried out. (1) Intermediate (III) 7.1g, before

The intermediate (LvnR rg J τ j strand WVi) prepared in (1) is 5.6 g, palladium acetate ruthenium 35 g, tributyl phosphine 1.34 g and sodium tributoxide 2 罘-A are added to 200 ml of four-burning Incidentally, 70 ml of 1 cf of 50 ml of dehydrated dimethyl 1 Rn 彳 彳 was added thereto, and the mixture was refluxed for 1.5 hours under a nitrogen gas stream. Pour the reaction solution into ^, U f know 50 〇 ml, filter out the precipitated solids, and then make it straight! Product, ........two dry. Compound (LV) Compound of formula 27 (8) was obtained as a crude product (yield: 81%). The obtained crude product μ was purified by a Shixi hose tube chromatography, and then sublimed fine. Elemental analysis of this compound (Perkin Ει·, 简 咖 〇 ) 、 、 、 、 、 、 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The results of the analysis of the product are shown below. Elemental analysis result: Calculated value (%) as C48H34FN3: c: 85.82 11:5.10 Measured value (%): C: 85.75 Η: 5·12 F: 2.80 N: 6.35 &lt;Example 19&gt; [Compound (19) Manufacture] Compound (19) (a compound represented by the compound (lix) in the following formula 28) is produced according to the following synthetic scheme shown in &lt;28. Equation 28 319365 139 200806626

3-bromo-9-biphenylcarbazole is described in the method described in the rank 4 (method of the formula 2), and the second embodiment of the first embodiment (2) The method (the odorophenyl carbazole in the formula 2, and the method of producing the intermediate (LVIII). The method of the work) is carried out in the same manner. (2) The production of the compound (19) is carried out in the above-mentioned Example 1 (1) #二述 (1) The intermediate (LVIII) 6 ^ ^ (1) 1) 7 · 1 §, the former tributyl (10) and the third butanol NZ were added to a 200 ml four-necked flask, and Adding dehydrated xylene 5 〇Μ and heating it back to 5 small days under a nitrogen gas stream. The reaction solution was poured into a methanol 5 towel, and the precipitated solid was taken out and dried under vacuum. 8.8 g of the crude product of the compound (10)) (= compound U9)) was obtained (yield: the obtained crude product was purified by a silica gel column chromatography, and then subjected to sublimation purification. Elemental analysis of this compound (manufactured by Perkin Elmer Co., Ltd., model 2CHN0/0), j-NMR, and 13C-NMR (manufactured by JEOL Ltd., gsx_27〇w) were analyzed to confirm that it was compound (19). The result of elemental analysis of the product. Elemental analysis result·· as C54H39N3 319365 140 200806626 5. 76 6. 00 Calculated value (%) ·· C : 88.86 Η: 5.39 Measured value (%) : C : 88. 72 Η : 5.28 <Example 20> [Production of Compound (20)] According to the synthetic scheme shown in the following formula 29 (the compound represented by the compound αχ(1) in the following formula 29) is broadened, "Do not (10)) Formula 2 9

Using Ν-(4-cyanophenyl)-indole-phenylamine, the method of the method (the method of the formula): 1 operation, the intermediate (10) was produced. (Method in Formula 1) The same procedure as in the production of (2) intermediate (LXI) & aniline in place of aniline in the above-mentioned (1) (2) 3, + (white ^ (^ 2 = + phenyl), and the same procedure as in the compound (10) (3) described in (2) of Example 1 to produce an intermediate _. The ten-part (LX) obtained in the above (1) 7.5g, 319365 141 200806626 obtained in the above (2): interstitial (Ul) 5.7g, succinic acid citrate 35β, tri-tert-butylphosphine h34g and first butyl g pre-sodium 2· 〇g added 2 In a four-necked flask of 〇〇ml, and adding 50 ml of dehydrated xylene to the mixture under reflux with nitrogen gas for 1.5 hours. The reaction/night was poured into 5QQml, and the precipitated solid was removed by filtration and then allowed to be hot. The crude product of the compound (LXII) (=compound (20)) in the formula 29 was obtained in 7.3 g (yield: 65%), and the obtained crude product was purified by a silica gel column chromatography. Sublimation purification was carried out, and elemental analysis of the chemical substance (manufactured by Perkin Elmer Co., Ltd., 24001 1 CHN0 / 〇 type), H-NMR, 13c-匪R (made by JEOL, gsx-270W) It was confirmed that it was compound (20). The following is the result of elemental analysis of the product. Elemental analysis result: Calculated value (%) as C49H32N6 : c : 83· 50 Η : 4· 58 N ·· 11. 92 Measured value (%) : C : 83. 45 Η : 4. 48 Ν : 12. 07 <Example 21> [Production of Compound (21)] A compound (21) was produced according to the synthesis scheme shown in the following Formula 30 (21). (a compound represented by the compound (LXIV) in the following formula 30).

(1) The intermediate (LXIII) was produced by using 1,4-bis(4-iodophenyl)benzene in place of the above-mentioned Example 1 (1) 142 319365 200806626, and the same operation as in the method) 4, 4 in the method (method of Formula 1), the method described in (1) of Example 1 (manufactured by Formula 1 to produce an intermediate (LXIII). (2) Compound (21) 84 g of the intermediate (LXIII) obtained in the above (1), 5.3 g of the intermediate (VI) obtained in the above (1), palladium acetate, 35 g, tri-tert-butyl lin, 1.34 g, and Tributyl alcohol sodium 2. 〇g was added to a 2 〇〇 ml four-necked flask, and 5 〇 ml of dehydrated xylene was added thereto, and 70 hot reflux was added for 1.5 hours under a nitrogen gas stream. The reaction liquid was poured into methanol 5 〇. In the 〇ml, the precipitated solid was taken out by filtration, and then dried under vacuum to give a crude product (yield: 62%) of the compound (α) (v) (~ Compound (21)). The obtained crude product was purified by a gel column chromatography, and sublimation was carried out. It was confirmed by elemental analysis (manufactured by Perkin Elmer Co., Ltd., 24〇〇11 CHN0/0 type), W-NMR, I3c-NMR (manufactured by JEOL Ltd., GSX-270W) to confirm the compound (21). The result of the elemental analysis of the product is shown below. Elemental analysis result: Calculated value (%) as C54H39N3 : C : 88. 86 Η : 5. 39 N : 5. 76 Measured value (%) : C : 88· 76 Η : 5. 28 Ν : 5. 96 &lt; [Example 22] [Production of Compound (22)] Compound (22) (a compound represented by the compound (lxvi) in the following formula 31) was produced according to the synthesis scheme shown in the following formula 31. 31 143 319365 200806626

The use of 1,4-bis (4- 峨 蔡-卜基, 土 '本Μ instead of arrows, ~ (1) method (method in formula 1) The method described in the above (1) (Formula 4=4'4~diiodobiphenyl, and the intermediate (LXV) is produced). The same operation is carried out. (2) Production of the compound (22) 1.34 g of the intermediate (LXV) butylphosphine prepared in the above (1) and 2. 〇g of the third butanol were added to a four-necked flask of 2 〇〇mi' and dehydrated diphenylbenzene was added thereto. Πα, heated under reflux for 1.5 hours under a gas stream. The reaction solution was poured into 5 mL of methanol, and the precipitated solid was removed by filtration, and then subjected to hot vacuum drying to obtain the compound αχνι in the formula 31. The crude product of 22)) was 7.4 g (yield 56%). The obtained crude product was purified by a gel column chromatography, and sublimation was carried out. The compound (22) was confirmed by elemental analysis (manufactured by Perkin Elmer Co., Ltd., 2400 II CHN0/0 type), NMR, and 13C-Li R (manufactured by JEOL Ltd., GSX-270W). The result of the elemental analysis of the product is shown below. Elemental analysis result: as c62h43n3 144 319365 200806626 . Calculated value (%) ·· C ·· 89· 72 Η : 5. 22 Ν : 5. 06 Measured value (%) ·· C ·· 89· 65 Η : 5. 38 Ν : 5. 03 <Example 23> [Production of Compound (23)] The compound (23) (the compound represented by the compound (LXVIII) in the following formula 32) is produced according to the synthesis scheme shown in the following formula 32. Equation 32

(1) The intermediate (LXVII) was produced by using Ν-(4-diphenylaminophenyl)-indole-phenylamine in place of the method described in the above (1) of the first embodiment (method of the formula i) In the same manner as in the method (1), the intermediate (LXVII) was produced in the same manner as in the method described in the above (1). (2) Production of Compound (23) The intermediate (Lxvn) obtained in the above (I) t (1×g), the intermediate (VI) obtained in (2), 5 3 g, acetic acid (tetra), and di-butylene h 34g and third butanol 2. 〇g is added to 2_: brother; &quot;, and added to the peeling-field #" ^ four-necked flask," 5 hearts A 501111, heated under a stream of nitrogen Drive and catch. The reaction solution was poured into 500 ml of methanol, and the solid was taken out and then dried under vacuum. The crude product of the formula 4 = 319365 145 200806626 (= compound (23)) was obtained in 5.6 g (yield: 43%). The obtained crude product was purified by a gel column chromatography, and sublimation was carried out. Elemental analysis (Perkin Elmer Co., Ltd., Μ(10) 11 C_/0 type), H-NMR, and (manufactured by Nippon Electronics Co., Ltd.) was used for the analysis of the compound (23). The results of the elemental analysis of the product are shown below. ' Element is the result of analysis · Calculated value (%) as C8GH44N4 : C: 87.77 H: 5.40 N: 6.82 Measured value (%) : C: 87.70 Η : 5.59 Ν: 6ί71 <Example 2 4 &gt; [Compound (24) Manufacture] A compound (a compound represented by the compound (LXX) in the following formula 33) is produced according to the synthesis scheme shown in the following formula 33. Equation 33

(1) The production of the intermediate (LXIX) is carried out by using -dimethyl- 4,4,di-diiodobiphenyl, the method described in (1), and the two examples described in (1) Method (Formula - Break = Same operation, manufacture of intermediates αχίχ). Method) 319365 146 200806626, (2) Production of Compound (24) The medium n spine obtained in the above (1)

^ 伃妁 intermediate (UIX) 7. 8g, intermediate (Vl) 5.4g prepared in the above Example J (2), acetic acid, 〇.35g, tris(1): phosphine L34g and third butanol 2, Add the chest four: burn two ^ in it plus dehydrated xylene _, and add back to the nitrogen gas for two 1.5 hours. The reaction solution was poured into a methanol 5 towel, and the precipitated solid was taken out by filtration, and then the pot was placed in a straight line. The crude product of the compound axx) (-compound (24)) in the formula 33 was 46 g (yield 42%). The obtained crude product was purified by a Shixi hose column chromatography, followed by sublimation purification. It was confirmed by elemental analysis (manufactured by Perkin Elmer Co., Ltd., 24 〇〇 11 c 〇 / 〇 type), lH_NMR, 13c_NMR (manufactured by JEOL Ltd., Gsx_27〇w) to confirm the compound (24). The result of the elemental analysis of the product is shown below. The element is the result of the analysis. Calculated value (%) as C5〇H3sN3 : c : 88· 07 Η : 5. 77 Ν : 6. 16 Measured value (%) : C ·· 88. 20 Η : 5. 58 Ν ·· 6. <Example 25> [Production of Compound (25)] The compound (25) (the compound represented by the compound (LXXIII) in the following formula 34) is produced according to the synthesis scheme shown in the following formula 34. 34 147 319365 200806626

(1) Manufacture of intermediates (LXXI)

3, 3 diiodobiphenyl is used instead of the method of the first # ^ method (method of the formula 1), and the method described in (1) of the first embodiment (1) is used. The squamous semi-diiodobiphenyl in the oxime, and the intermediate of the example 1 (LXXI). The same operation was carried out, and the production of the intermediate (2) intermediate (LXXII) was carried out using 3-bromo-9-(1-naphthyl). The method described in the sputum (method in the formula 2) / the above-mentioned implementation (1) (2) ^ t , Μ, Π ^ (2) „ ^ (^ 2 t ^ ^ ^

Preparation, production of intermediates (LXXII). 'Dingtong H (3) Compound (25) 7.2 g of the intermediate (J^CLXXI) prepared in the above (1), intermediate (LXXII) 6e2g obtained in the above (2), vinegar Clothes, 0, α ^ aQ 夂 palladium 0.35g, tri-tert-butyl phosphine 1.34g and sodium third butanol 2. 〇g added? Nn〗 g was added to a 20 〇W four-necked flask, and dehydrated xylene 5 〇mi was added thereto, and heated under reflux for 1.5 hours in the upper y. The reaction solution was poured into 5 〇〇ml of sterol, and the precipitated solid was removed by filtration.

After that, it was allowed to dry under vacuum. 3.5 g (yield 31%) of the crude product of the compound (LXXIII) (= compound) of the formula W in the formula 34 was obtained. The obtained crude product was refined by a Shixi rubber column chromatography and then subjected to sublimation purification. 319365 148 200806626 It was confirmed by elemental analysis (manufactured by Perkin Elmer Co., Ltd., 2400 1 1 CHN0/0 type), NMR, and 13C-NMR (manufactured by JEOL Ltd., GSX-270W) to obtain the compound (25). The results of the elemental analysis of the product are shown below. Element 5 analysis result · Calculated value (%) as C52H37N3 ·· C : 88· 36 Η : 5. 30 Ν : 5. 97 Measured value (%) : C ·· 88. 55 Η : 5. 28 Ν : 6.实施 <Examples 26 to 30> According to the same synthesis method as in Example 25, the compounds (26) to (30) were synthesized. The elemental analysis results of the products are shown in Table 34. [Table 34]

In the embodiments shown below, if there is no particular preset limit, then the mix is all indicative of the weight ratio. The steamed ore (vacuum-steamed ore) is fed at about the same time, without substrate heating or cold temperature (4). Further, the characteristics of the organic EL element evaluated in the light-emitting characteristics of the 7G member. Polar area 2 sides 2_ <Example 31> The compound (1) 319365 149 200806626 was vacuum-deposited on the washed glass plate with the ITO electrode to obtain a hole injection layer having a film thickness of 60 nm. Next, n, n, f diphenylamino-4-phenyl)-N,N,-diphenylbenzidine was plated with a real jade to obtain a hole transport layer having a film thickness of 2 〇 nm. Further, a ruthenium (9)-fluorene fluorinated aluminum complex was vacuum-deposited to form an electron-injection-type light-emitting layer having a film thickness of 60 nm, on which lithium fluoride was first deposited, followed by vapor deposition of aluminum to form an electrode. After that, an organic EL element was obtained. <Examples 32 to 60> An organic EL device was produced in the same manner as in Example 31 except that the compounds (2) to (30) of Tables 1 to 3 were used instead of the compound (1) of the hole injection layer. The elements of Examples 31 to 56 were placed in an environment of room temperature and i 〇〇 ° C:, and their luminance was measured by allowing them to be emitted at a current density of 10 mA/cm 2 for a certain period of time. The results are shown in Table 35. 150 319365 200806626 [Table 35] Example compound initial voltage (V) Initial luminance (cd/m2) Room temperature, 1,0 0 hour brightness (cd/m2) 100 〇C, 1,000 hours of brightness (cd /m2) 31 (1) 5.1 430 410 387 32 (2) 5. 5 410 390 360 33 (3) 5.6 360 355 345 34 (4) 5. 0 500 450 425 35 (5) 4. 5 450 420 400 36 (6) 5. 0 410 388 366 37 (7) 5. 2 400 385 363 38 (8) 4. 9 360 356 345 39 (9) 5.1 410 405 370 40 (10) 5. 3 380 375 360 41 (11 5· 0 390 380 365 42 (12) 4. 8 400 388 360 43 (13) 5. 5 480 450 435 44 (14) 5.1 430 420 410 45 (15) 5. 0 460 450 420 46 (16) 4 8 430 420 410 47 (17) 5. 0 380 365 338 48 (18) 5. 2 350 340 325 49 (19) 4. 6 290 264 250 50 (20) 5. 6 250 240 230 51 (21) 5 1 420 400 365 52 (22) 5. 0 410 405 378 53 (23) 5. 2 400 390 370 54 (24) 5. 1 360 385 360 55 (25) 5, 2 380 410 370 56 (26) 5 1 410 385 340 57 (27) 5. 2 400 390 370 58 (28) 5. 3 480 450 398 59 (29) 4. 6 460 450 420 60 (30) 4. 9 410 400 410 151 319365 200806626 4 Example 61 &gt; with IT 0 The seat ί J. Matchmaker is not powered on glass plate, copper phthalocyanine vapor-deposited to form a film having a thickness of 25nm hole injection layer. 1 Today, , 9 /, _ people make the compound (19) of Table 2 and the compound (A) shown below

Co-deposition was carried out at a composition ratio of 100:8 to form a light-emitting layer having a film thickness of 45 nm. Further, the compound (B) of Lithium was vapor-deposited to form an electron injecting layer having a thickness of 2 Å. An organic electroluminescence device was obtained by depositing 1 nm of lithium oxide (LhO) thereon and vapor-depositing aluminum (Al) to form a cathode. This component exhibits an external quantum efficiency of 6.5 % at a DC voltage of 10V. Further, the half life of driving at a constant current of 150 (cd/m2) is 5,000 hours or more. <Examples 62 to 68> An organic El element was produced in the same manner as in Example 61 except that the compound shown in the following Table 36 was used instead of the compound (19) of the light-emitting layer. The components of Examples 62 to 68 were placed at room temperature and 1 Torr, and were subjected to a current density of 10 mA/cm 2 for a certain period of time and luminescence to determine the degree of 319365 152 200806626. The results are shown in Table 36 [Table 36]

<Example 69> On a glass plate with a ΙΤ0 electrode, a compound (C) as shown below was used.

After plating to form a hole injection layer having a film thickness of 60, the compound (13) of Table 2 was plated to form a hole transport layer having a film thickness of 20 nm. Next, Alq3 is vapor-deposited to form an electron injecting light-emitting layer having a film thickness of 6〇nra, and a vapor-deposited (10) fluorination clock is vacuum-deposited to form a cathode (10) to form a cathode. Electroluminescent element. The luminous efficacy of this component in the DC voltage of 5V is "^lm/W". Further, the half-life of driving at a constant current of 5 〇〇 (cd/m2) at room temperature was 5 hours or more. 319365 153 200806626 <Examples 70 to 72> An organic el element was produced in the same manner as in Example 69, except that the compound shown in Table 37 below was used instead of the compound (13) of the hole-passing layer. The elements of Examples 64 to 67 were placed at room temperature and (10). The shell of the c was measured at a current density of 10 mA/cm 2 for a certain period of time and luminescence. The results are shown in Table 37. [Table 37]

<Example 73> On a glass plate with a ΙΤ0 electrode, N,N,-bis(4,-diphenylamino phenyl)-U,-diphenylbenzidine was distilled (four) to obtain a film thickness of 40 rm. The electric/same main entry layer. Next, the compound (1) of Table 1 and the compound (D) shown below are made.

The light-emitting layer having a film thickness of 40 was formed by co-evaporation at a ratio of 98:3, and then Alq3 was vacuum-deposited to form an electron injection layer having a thickness of 3 Å. At 319365 154 200806626, an organic electroluminescent device was obtained by vacuum-depositing 1 nm of lithium fluoride and then vacuum-depositing aluminum at 2 〇〇 nm to form an electrode. This element emits light having a luminance of 35 〇 (cd//m 2 ) and a maximum luminance of 766 (in / m) at a DC voltage of 5 V. Further, the half life of driving at a constant current of 5 〇〇 (cd/m2) was 4 hours. <Examples 74 to 75> An organic EL element was produced in the same manner as in Example 73 except that the compound shown in the following Table 38 was used instead of the compound (1) of the light-emitting layer. The components of Examples 68 to 70 were placed in an environment of room temperature and i〇〇t, and their degree was measured by allowing them to continue to emit light at a current density of 1 OmA/cm 2 for a certain period of time. The results are shown in Table 38. [Table 38] Example compound initial voltage (V) Initial luminance (cd/m2) &quot;450&quot; Room temperature, 1,000 hours of brightness (cd/m2) 420 74 Τδ&quot; l〇〇°C, 1, 〇 〇〇 hours of brightness (cd/m2) Tl? (24) 725) 390&quot;ΪΊΤ 360 400 340 &quot;367 <Example 76> On a glass plate with an IT0 electrode, pED〇T//pss (3,4-Dethylhexyloxy)-2,5-thiophene/polystyrenesulfonic acid) A film having a film thickness of 60 nm was formed by a spin coating method. Further, the compound (3) of the surface oxime and the above-mentioned compound (A) were dissolved in a toluene solvent at a composition ratio of 100:8 and applied by a spin coating method to prepare a light-emitting layer having a film thickness of 5 Å. On the coated substrate, the above compound (B) was deposited by vacuum plating to form a 319365 155 200806626 electron injection layer having a film thickness of 2 〇 nm. An organic electroluminescence device was obtained by vapor-depositing 1 η π of lithium oxide (Li 2 〇) thereon and then distilling it to 20 nm to form a cathode. This component exhibits an external quantum efficiency of 5.3 at a DC voltage of 10 volts. Further, the half life of the constant current driving at a light-emitting shell of 100 (cd/m2) is 5,000 hours or more. <Examples 77 to 86> In addition to the use of the compound (6), the compound (8), the compound (9), the compound (1〇), the compound (18), the compound (η), and the compound (22) in Tables 1 to 3. Compound (24) and Compound (25) Compound (27) were prepared in the same manner as in Example 76 except for the compound (3). These devices have a half-life of more than 5,000 hours when driven at a constant current of 1 〇〇 (cd//m2) at room temperature. <Example 8 7> On a glass plate with an ITO electrode, HIM9 in Table 5 was vapor-deposited to form a hole injection layer having a film thickness of 50 nm, and then the compound (1) was plated at 2 〇 nm to form electricity. Hole transport layer. Further, Alq3 was further vapor-deposited to form a light-emitting layer having a film thickness 汕(10). Further, the compound Εχ3 in Table 15 was distilled to form an electron injecting layer having a thickness of 〇nm. An organic EL element was obtained by vapor-depositing an oxidation clock of 1 nm thereon and then steaming it to form a cathode. This component shows a luminance of 72 〇 (cd/V) in DC M 5.GV. In addition, the half-life of the element immediately after the element was fabricated and after 15 hours of storage in the oven of rc was driven at a constant current of 5 〇〇 (cd/V) at a temperature of 5,000 hours. [Examples 88 to 1〇2] 319365 156 200806626 As the electron injecting layer, the compound i5 to the compound of the formula i2 to the compound i2 to the compound Π16 in the silk i5 to the table i8 was used in place of the compound book, and the example 87 was prepared. The components were fabricated under the same conditions. For the components that were just made in the component 4 and in the oven at 150 t, the component properties were measured: the result was 'any element at a current density ("drive, 蚪 το pieces The characteristic 'is all electric 4. 4. 以下 (7) or less, brightness 5 (10) (Μ / 〆) = ' and the half-life of the constant current drive is 5, 0 with a luminous intensity of 5 〇〇 (cd/m2) at room temperature. 〇〇hours or more. <Examples 103 to 114> In addition to the use of the compound (8), the compound (9), the ruthenium (1 〇), the compound (11), the compound (13), and the compound in Tables 1 to 3. (14), compound (15), compound (16), compound (21), compound (27), The compound (28) and the compound (3) were prepared in the same manner as in Example 87 except that the compound (1) was used instead of the compound (1), and it was stored for 2 hours after being newly formed into an element and in an oven of 150 C. The characteristics of the device, the characteristics of the device: the result is that the component characteristics of any device driven at a current density of 10 (mA/cm2) are voltages of 4. Q(v) or less, and brightness is 5 (10) (6) eight or more). The half-mourning period of the constant current driving at a room temperature of 5 〇〇 (cd/m 2 ) was 5 〇〇〇 hours or more. <Example 115 &gt; On a glass plate with an ITO electrode, After HIM1 in Table 6 was vapor-deposited to form a hole injection layer having a film thickness of 55 nm, the compound (9) was vaporized 2, and Jm was formed to form a hole transport layer. Further, Alq3 was vapor-deposited to form a film. A light-emitting layer having a thickness of 2 Å. Further, the compound ΕΤ3 in Table 15 is evaporated to form an electron 'main entrance layer having a film thickness of 319365 157 200806626 3^0mn. An oxidation clock of 1 nm is vaporized thereon (l "〇 After the aluminum ΙΟΟηηι is further evaporated to form a cathode, an organic germanium element is obtained. This element shows 680 (C(W) in a direct current voltage of 5V). In addition, for the element and the piece which are stored in the oven immediately after the component is placed in the oven at 15 () t, the constant current is driven at room temperature with a luminance of 5 〇〇 (cd/m 2 ). The half-lives are all above 5,000 hours. <Examples 116 to 12 8 &gt; In addition to the electron injecting layer, the compound ET2, the compound ET4, the compound ET6, the compound ETg, the compound mu, the compound in Tables 19 to 23 are used. From the range of ΕΠ2 to ΕΤ14, the compound ΕΤ16 to the compound ετ2〇 was replaced by the same conditions as in Example 115 except for the compound ΕΤ3. For the component just after the component is fabricated and at 15 (the oven of rc, the component of (4) the component is used. As a result, the component characteristics of the component when driven with an electric scratch of 10 (mA/cm2) All have a voltage of 4. 〇 (ν) or less, a degree of acceptance of 500 (Cd/m2) or more, and a half-life of 5,000 hours when the illuminating brightness is 5 〇〇 (cd/m2) at room temperature for constant current driving. <Example 129> On the glass plate with the ιτο electrode, the white enamel in Table 6 is used: after forming a hole injection layer having a film thickness of 6 -, the compound (10) is vapor-deposited - = into a hole transport Further, a layer of a thickness of 2_ is formed by steaming. Further, the compound ES5 is vapor-deposited to form an electron having a thickness of 3 〇 nm, and is poured into the layer, and an oxygen test of 1 nm is evaporated thereon. Evaporation of l_m and the shape of the cathode is paid to the organic EL element. This element shows the luminous efficiency of UUm/W in DC voltage 5. Moreover, when the 7L piece which was stored in the oven of 319365 158 200806626 and the 150 C immediately after the preparation of the element was driven at a constant current of 5 GG (Cd/m2) at room temperature, The half-life is more than 5,000 hours. <Example 130> On the glass plate with the ΙΤ0 electrode, the compound (9) was dissolved in 1,2-dichloroethane, and a hole injection layer having a film thickness of 5Q (10) was formed by a spin coating method. Next, Alq3 is evaporated to form an electron injecting light-emitting layer having a thickness of 3{) nm, and an electrode having a film thickness of 100 nm is formed thereon by an alloy of magnesium and silver in a ratio of 1 G:U. . The component's payout rate in the DC voltage uv is 3.Gnm//w). Further, the half-life at the time of constant current driving at a luminance of 5 〇 0 (cd/m 于 at room temperature was 5 〇〇〇 hrs or more. <Example 131> Thickness of film formed on a glass plate with an IT0 electrode 35nm hole injection layer. Secondly with Alq3

The compound (12) was deposited by vapor deposition. The compound (F) shown below was co-deposited at a composition ratio of 1:50 to form a light-emitting layer having a thickness of 4 Å. Further, Alq3 was further vapor-deposited to form an electron injecting layer having a film thickness of 3 〇 nm. On this, an element was formed by vacuum-depositing lithium fluoride (LiF) 1 nm, and then vacuum-depositing aluminum (A1) 319365 159 200806626 2 = to obtain an element. This component has a luminous efficiency of 5 〇v = at a DC voltage. Further, the half life of driving at a constant current of 5 〇〇 (cd / m) is 5 hours or more. <Example 132> On the glass plate with the ΙΤ0 electrode, the compound (10) and the compound and 14) were co-distilled at a composition ratio of 1:1 to form a hole/main layer having a film thickness of 6 Gnm. Next, the compound (G) shown below

The light-emitting layer having a film thickness of 2 〇 nm was formed by vapor deposition. Further, Alq3 was further vapor-deposited to form an electron injecting layer having a film thickness of 20 nm. Lithium fluoride (LiF) 1 nm was vacuum-deposited thereon, and aluminum (A1) was vacuum-deposited at 2 〇〇 nm to form an electrode, thereby obtaining a component. This component shows a luminous efficiency of 3 〇 (lm/w) in a DC voltage of 5 〇 v. Further, the half-life of driving at a constant current of 5 〇〇 (cd/m2) is 5,0 0 hours or more. <Example 133> A compound (7) was vapor-deposited on a glass plate with a ΙΤ0 electrode to form a hole injection layer having a film thickness of 60 nm. Next, the compound (η) shown below and the compound (I) shown below 160 319365 200806626

Coherent deposition was carried out at a composition ratio of 20:1 to form a light-emitting layer having a film thickness of 2 〇 mn, and then Alq3 was distilled to form an electron injection layer having a film thickness of 2 〇 nm. An element was obtained by depositing lithium fluoride (LiF) at a thickness of 1 nm on the vacuum, and then vacuum-depositing the aluminum to 200 nm to form an electrode. This component shows a luminous efficiency of 6·0 (lm/W) at a DC voltage of 5.0 V. Further, the half life of driving at a constant current of 5 〇〇 (cd/m 2 ) is 5 hours or more. <Example 134> On the glass plate with the ΙΤ0 electrode, the compound (13) was distilled to form a hole injection layer having a film thickness of 45 nm. Next, the compound (1) shown below and the compound (K) shown below are 319365 161 200806626

Compound (j)

The H3C compound (K) was used to form a light-emitting layer having a thickness of 4 Gnm by a common plating, and was further deposited by Alq3 to form an electron injection layer having a thickness of 3 Å. On top of it, a fluorination clock (LiiOlnm = &gt; r b , U) 111 &quot;1 was vacuum distilled, and then aluminum was vacuum-deposited at 200 nm, and the electrode I _ pieces were transferred to the crucible. This component shows the luminous efficiency of ^Ujn/W in DC current i 4. Further, when the driving current is driven by the illuminating luminance of cd/m2, the half life is 5 hours or more. &lt;Example 135&gt; The compound (8) was steamed on a glass plate with a ΙΤ0 electrode to form a hole injection layer having a positive thickness of 1. Next, make the compound shown below (6)

And Alq3 is co-evaporated at a composition ratio of 1.1 to form a film having a film thickness of π (4). 319365 162 200806626 A light-emitting layer. Further, after the electrode of the film thickness (10) is formed by adding 5 gold in which magnesium and silver are mixed with i:3, the luminous efficiency of 2 birds/heart is shown in the voltage of 〇V. . Also:: The constant current flooding time is 5,000 hours or more at a temperature of 5 〇〇 (cd/V). <Example 136> The compound (12) was vapor-deposited to form a hole injection layer having a film thickness of 50 nm on the glass plate with the ΙΤ0 electrode. Second, the following compounds (Μ)

The compound (Μ) was co-evaporated at a composition ratio of 100:1 to form a light-emitting layer having a film thickness of 25 nm. Further, BCP was further vapor-deposited to form an electron injecting layer having a film thickness of 25 nm. After the distillation clock (Li) 0·5 nm ' was evaporated and the silver was distilled to i50 nm, the element was obtained. This element shows a luminous efficiency of 丨·5 (lm/W) at a DC voltage of 8·0V. Further, the half-life at the time of constant current driving with a light-emitting luminance of 500 (cd/m2) is 5,0 0 or more. <Example 137> The compound (15) of the present invention was vapor-deposited on a glass plate with an ιτο electrode to form a hole injection layer having a film thickness of 40 nm. Next, 163 319365 200806626 • Compound (N) shown below was vapor-deposited at 10 nm to form a hole transport layer. Further, the compound (0) shown below and the compound (p) shown below are further shown.

F compound (ΝΓ> compound (Ο)

The compound (P> was co-deposited at a composition ratio of 1:9 to form a light-emitting layer having a film thickness of 25 nm. Next, BCP was vapor-deposited to form a hole blocking layer of i5 nm.

Alq3 was vapor-deposited to form an electron injecting layer having a film thickness of 25 nra. Lithium fluoride (LiF) was deposited thereon to a thickness of 1 nm, and aluminum was vapor-deposited to a thickness of 100 nm to form a cathode. This component exhibits an external quantum efficiency of 8·〇% at a DC voltage of 8V. Further, the half-life at the time of constant current driving with a light-emitting shell degree of 200 (cd/m2) was 5,000 hours or more. <Example 138> The compound (1〇) 319365 164 200806626 of the present invention was vapor-deposited at 60 nm on a glass plate with an ιτο electrode to form a hole injection layer. Further, Alq3 was further vapor-deposited to form a light-emitting layer having a film thickness of 20 nm. The compound shown below (Q)

The compound (Q) was vapor-deposited to form an electron injecting layer having a film thickness of 30 nm. Lithium oxide (LhOMnm was deposited thereon, and aluminum was vapor-deposited by 1 〇〇 nm to form a cathode, and an element was obtained. This element showed a luminous efficiency of 33 (lm//w) at a DC voltage of 4.0 V. The half life of driving at a constant current of 500 (cd/m 2 ) is 5,0 0 0 or more. <Examples 139 to 145> In addition to using ESI 1 and EP 2 in Tables 24 to 33 as electron injection layers The experiment was carried out in the same manner as in Example 138 except that the compound (Q) was replaced by the above compound (Q). For the copper component and the component in the baking phase of 150 C for J hours. The characteristics of the element were measured in the same manner as in Example 1. As a result, the element characteristics when any element was driven at a current density of 1 KmA/cm 2 ) were voltages of 4 〇 (fantasy, 500 degrees (cd/m). The above half-times when the constant light driving is performed at room temperature in a luminance of 5 〇〇 (cd/m 2 ) _, _ hr or more. <Example 14 6 &gt; As in a glass plate with an ιτ〇 electrode In the above, the compound (2) of the present invention is treated to form a hole injection layer having a thickness of 35 nm, and 319 in Table 1 365 165 200806626, the HTM9 is deposited by vapor deposition to form a hole transport layer having a film thickness of 2〇ηπ1. Next, the compound (R) shown below and the compound (S) shown below have a composition ratio of 5〇:1. Co-deposition was carried out to form a light-emitting layer having a film thickness of 35 rm. Further, the compound (T) shown below was further added.

The ruthenium plating was performed to form an electron injection layer having a film thickness of 3 〇 nm. On this, an element was obtained by vacuum-depositing lithium fluoride (LiF) at a thickness of 1 nm, and then vacuum-depositing aluminum at 2 〇〇 nm to form an electrode. This element exhibits a luminous efficiency of 5. 〇 (lm//w) in a DC voltage of 3·5 ν. Further, the half life of driving at a constant current of 5 〇〇 (cd/m2) is 5,000 hours or more. <Examples 147 to 153> In addition to the use of the compound (4), the compound (8), the 166 319365 200806626, the compound (12), the compound (15), the compound (19), and the compound (22) in Tables 1 to 3, respectively. And. The material (26) was replaced with the same compound as in Example 146 except for the compound (2). As a result, the element characteristics when the device is driven at a current density of j 〇 (10) / cm 2 ) are voltages of 4 〇 (v) or less, luminance of 5 〇〇 (cd/m 2 ) or more, and luminance of 5 〇. The half-life of 〇(cd/m2) driven at room temperature is 5, more than 〇〇〇 hours. <Comparative Example 1> An organic EL device was produced in the same manner as in Example 31 except that the following compound (U) was used instead of the compound (1) as the hole injection layer.

Q compound (u&gt; <Comparative Example 2> An organic E]L element was produced in the same manner as in Example 31 except that the following compound (V) was used as the hole injection layer instead of the compound (1).

Compound (v &gt; 167 319365 200806626 » w The components of Comparative Example 2 were placed at room temperature and 100 atmospheres, and their current density was measured at a current density of (4) / (10) 2 for a certain period of time and luminescence to determine the degree of exemption. It is shown in Table 39 below. [Table 39]

4 and Table 39, it can be seen that the element made using the compound of the present invention can be used for a lower initial voltage and a longer life than the element made by using the compound (V) in the comparative example. Higher brightness. As described above, by using the amination of carbazole shown in the present invention, a high performance EL element can be obtained. In addition, it is understood that a comparative compound having a substituent with respect to nitrogen = can exhibit a higher level of shame and achieve a lower driving voltage and longer life of the organic EL device. BRIEF DESCRIPTION OF THE DRAWINGS The image of f 1 is a 1H-NMR spectrum of the compound (1). (The THF one center = 2 figure is the 1H-NMR spectrum of the compound (2). (H-NMR spectrum of the compound (7) in Figure 3 of THF-d8. (THF-d8 319365 168)

Claims (1)

200806626 X. Patent application scope: It is expressed by the following general formula [1]··1· A kind of amine compound containing carbazole General formula [1] = Medium [2/ means "cutting type (1) table (four) ten sitting base (wherein, Ar5 represents a sulphur (tetra) group having a carbon number of 6 to fluorene which may have a substituent, or a valence of a carbon number of 2 to 18 which may have a substituent: a group, and R to R each independently represent a hydrogen atom , halogen atom 5 monovalent organic residue); "to Ar4, independently, a carbon number of 6 5 1S Μ Μ - a group of a group D hydrocarbon group, may have a substituent: a monovalent heterocyclic group of 18 (only, The above formula [2] represents a case where a sitting group is excluded; A represents an alkyl group having a carbon number of from 1 to 30 which may have a substituent). 2. An amine compound containing the compound of the fourth aspect of the invention, wherein The Ar5 in the formula [2] is a phenyl group which may have a substituent 319365 169 200806626 represented by the following formula [5]: a formula [5] (wherein R38 represents a hydrogen atom, a self-priming atom, a cyano group, an alkyl group having a carbon number of 3, a monovalent aromatic furnace group having 6 to 12 carbon atoms which may have a substituent, and a carbon number which may have a substituent 2 to 5 monovalent heterocyclic groups). 3. The amine compound containing carbazole according to item 2 of the patent application, wherein R38 in the general formula [5] is a hydrogen atom, a halogen atom, a cyano group, a carbon number of 3 to a phenyl group, a phenyl group, Or 4-u is more than a base. 4. The carbazole-containing amine compound according to any one of claims 1 to 3, wherein R1 to R7 in the formula [2] are a hydrogen atom. 5. The carbazole-containing amine compound according to any one of claims 1 to 4, wherein the A group in the general formula [1] is a group having a carbon number of 1 to 5 or a halogen atom. Substituted 4, 4'-biphenyl, 3,3,_diphenyl which may be substituted by the alkyl group of 1 to 5 or a halogen atom, or a halogen group or a halogen which may have a carbon number of 1 to 5. a 2, 2'-terphenyl substituted by an atom, a 1,4-naphthyl group which may be substituted by a carbon number of 1 to 5 or a halogen atom, or an alkyl group which may have a carbon number of 1 to 5 Or a 1,5-anthranyl group substituted by a halogen atom. 6. The carbazole-containing amine compound according to any one of claims 1 to 4, wherein the A in the general formula [1] is represented by the following general formula [3]: 170 319365 200806626 Biphenyl formula [3] 'u, 虱原千, a halogen atom or a steroid residue' or an adjacent organic residue may form a ring with each other). For example, in the case of the amine compound containing the material in the sixth paragraph of the patent application, the A in the general formula [1] is the following 4, 4, - extension of the "^ Ί * 迷 通式 [ [ [ [ [ [ Base: General formula [4] Wherein 'R to IT denotes a hydrogen atom, a dentate atom or a monovalent residue, 1 and R33, R34 and R35, or R36 and r37, which may be bonded to each other to form a ring). &amp;&lt;&gt;&lt;&gt;&gt;&lt;&gt;&gt;&lt;/RTI&gt;&gt; Dif-group-4, 4'-extended biphenyl, 3,3,-extended biphenyl 319365 171 200806626 • 2, 2'-extended biphenyl. 9. For example, if you apply for a patent in the Fan Park, you can use the A system 4, 4' - the extension of the A. 4, 4' - the organic electro-initiating well. In the first to the ninth paragraphs, the 乂 含有 含有 含有 含有 含有 含有 含有 胺 胺 胺 胺 胺 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机, is a complex light-emitting element that forms a light-emitting layer between a pair of electrodes or forms a light-emitting layer, and at least one layer of the patent range Μ Γ Γ 有机The organic electroluminescent element or the hole transporting layer formed by the material of the organic electroluminescent element of 0 is: an organic electroluminescent element having a hole injection layer and / k layer, (3) and / or the hole transport layer of the hole is: 'The patent for the range of materials for organic electroluminescent elements, item 10 319365 172