TW201224109A - Benzo[c]carbazole compound having substituent including pyridine and organic electroluminescent device - Google Patents

Abstract

An organic electroluminescent device excellent in life-span and driving voltage is provided. An organic electroluminescent device is made by using a benzo[c]carbazole compound, having substituent including pyridine, as electron transport material.

Description

2012243⁄4 VI. Description of the Invention: [Technical Field] The present invention relates to a benzoate (4) carbazole compound having a pyridine substituent and an electron transfer material using the benzo[C]carbazole compound, Electromechanical excitation elements, display devices, and illumination devices. [Prior Art] No flaws, using the display device of Youyi

Various studies have been conducted to save power or reduce the thickness, and the organic electroluminescent device formed of the material has been actively studied because of its ease of weight reduction and enlargement. In particular, the development of an organic material having a light-emitting property including blue, which is one of the three primary colors of light, and the ability to transfer electrons (having become a semiconductor or a superconductor 2): an organic material? The development of the polymer compound and the low molecular weight: k, the active research has been carried out so far. σ 献 2, open the first side of the coffee manual: patent papers published 3 · ^ text A ® * f 'reported the shot 'time frame for the joint f', domain or turn to poor social peace 8 -_ bulletin 'patent literature 4, 曰 #=曰二 = No. Bulletin: Reading 5, Japan opened 201224109 "Patent Document 6". Also reported σ will contain. Card 3 ring and, for charge transfer (hole transport and electron transport patent Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Patent Document 7 Patent Document 8 Japanese Patent Laid-Open Publication No. 2003-146951, Japanese Patent Laid-Open Publication No. Publication No. 2007/086552, PCT Patent Publication No. 8-12600, No. PCT Patent Publication No. 2003- Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. a compound of scallions, aryl or heteroaryl groups < The combination of the naphthalene and the onion is the central skeletal sigma (4). There are several types of 3D card faces. However, these known compounds have an elemental driving voltage equal to the life of the device and an electron-transporting material which is excellent in light emission. In particular, the blue language has excellent characteristics of electricity;: The light transmission material is compared with the wheel material, and it is expected to develop an electron transport material suitable for improving the characteristics of 70 pieces of 201224109 ^oo/jpif ^ color light. In order to solve the above problem, the inventors have made the organic electroluminescence light of the organic layer of the sub-transport material "excellent in terms of life, and the present invention has been completed. The system has the following formula (1) - two

No [[= benzo[e] compound, which is represented by the following formula (1) (A-1) (A-2)

0)

(A-3) Silver δ (Α-4)

In the above formula (1), R is an aryl group having a carbon number of 6 to 24 or a carbon number of 2 to 2 Α and Α· is selected from the group consisting of the above formula and the formula, and the above formula (A-2) The group represented by the above formula (A_3), the group represented by the above formula (A-4), the group __=, the aryl group having a carbon number of 6 to 18, and the other structure, The ring contained in the ring may also be substituted with a carbon number of 1 to 6, which is a benzopyrene skeleton of the compound represented by the formula (1), and a 201224109.

^ W P ^ XX row replaces any of R, A and A, and any hydrogen in it can be replaced by deuterium. [2] The benzo[c]carbazole compound according to the above [1], wherein R is a group selected from the group consisting of the groups represented by the following formulas (R-1) to (R_2〇); Any one of A and A' is selected from the group represented by the following formula (A-1-1) to formula (a-1-3), and the following formula (A-2-1) to formula (a) -2-18) The base represented by the formula (A-3-1) to the formula (A-3-6), and the following formula () to (A-4-6) One of the groups formed by the base of the expression, and the other is a group selected from the group consisting of the groups represented by the following formulas (A-5-1) to (a-5-U), and the composition formula (1) Any of the R, Α, and Α' of the benzo-n-car π sitting skeleton of the compound represented by the compound may be substituted by gas, [Chemical 7] 201224109 J8〇/jpif

(R-1)

(R-2)

(R-10)

(R-15)

(R-16) (R-17) (R-18)

(R-19)

(R-20)

[化8] li:: 201224109. JOU l jyif Q- ^ o- (A-1-1) (A-1-2) (A-1-3) QQ- n^- QQ- C>^ 〇&lt ;v (A-2-1) (A-2-2) (A-2-3) (A-2-4) (A-2-5) (A-2-6)

I

(A-2-7) (A-2-8) (A-2-9) (A-2-10) (A-2-14) (A-2-15) (A-2-16)&lt ;QrQr l (A-3-1) (A-3-2) (A-3-3) (A-3-4) (A-2-11) (A-2-12) (A-2- 13)

(A-2-17) (A-2-18)

(A-3-5) (A-3-6)

(A-5-η (A-5-2) (A-5-3) (A-5-4) (A-5-5) (A-5-6) (A-5-7) (A -5-8) (A-5-9) (A-5-10) (A-5-11) 〇 [3] The benzo[c]carbazole compound according to the above [1], wherein R Any one selected from the group consisting of the groups represented by the above formula (JM) to formula (R-14), any one of A and A' is selected from the above formula (A-1-1) to (α_μ) ) 201224109 38673pif The base represented by the above formula (Α_2_υ~式(Α·2_18), the base represented by the above formula (Α-3-1)~式(α_3_6), and the above formula (A〆)) a group of groups represented by the formula (Α·4_6), and the other is selected from the group represented by the above formula (Α-5-1) and the above formula (Α_5_8)~ (5 And a benzo(4)-salt compound according to the above [1], wherein R is selected from the group consisting of the above formula (5)) to (R_U). One of the groups consisting of a group, and any one of A and A' is selected from the group represented by the above formula (A-Μ) to (A-^), and expressed by the above formula (AH) to (AMS). Based on the above formula (Α-3-1)~式(Α_3_6) And one of the group consisting of the group represented by the above formula (Α-4-3), and the other is selected from the group represented by the above < (eight-call) and the above formula d(4)~ -5-10) A benzo[c]carbazole compound according to the above [1], wherein R is the above formula (R-1), formula ( R_1G) or Formula (R_U, any of A and A' is selected from the formula (A-Μ)~ (A_卜3), and the above formula (4)])) ·2·4) The base represented by the above formula (Α_2-7)~式(Α_2_9), the base represented by the above formula (Α_2_ΐ2), the base represented by the above formula (Α_2_15), and the above formula (4) ])) The group represented by the formula (U-3-6) and the group of the group represented by the above formula (m) to the formula (Α_4_3), and the other one selected from the above formula (A- 5-1) One of the groups represented by the above formula (Α_5·8) and the group represented by the above-mentioned 201224109 ^oo/jpif (A-5-9). [6] The benzo[c]carbazole compound according to the above [1], wherein R is a group represented by the above formula (R-1) or formula (R_U), and any one of A and A is selected. The group represented by the above formula (A_M) to the formula (a small 3), the group represented by the above formula (A-2-1), the group represented by the above formula (a_2_2), and the above formula (A_2_7) to the formula (A_2_7). a group represented by a_2_9), a group represented by the above formula (A-2-12), a group represented by the above formula (A_3_1;) to formula (A_36), and the above formula (Hi) to formula (Α·4_3) One of the groups consisting of the bases represented by the group represented by the above formula (Ajq), the group represented by the above formula (Α·5_8), and the group represented by the above formula (A 5-9) One of the groups formed. m is a benzo[c]carbazole compound as described in the above π], which is represented by the following formula (1-335): [Chemical 9]

[8] The benzoxanthene compound according to the above [1], which has the following formula (1 140), formula (1_212), formula (1-431), formula (1-383), formula (1_384), (1-376), Formula (1_360), Formula (1-408), Formula (1-237), Formula (1_189), 201224109 j»o/jpif Formula (1-455) or Formula (1-59) Representation: [Chemical 10]

H: 1 11 201224109 JQO/jpif [9] An electron transport (4) containing the compound as described in the above (1) to [8m壬. [10] An organic electroluminescence device comprising: an electrode composed of an anode and a cathode; a light-emitting layer disposed between the pair of electrodes; and disposed between the cathode and the light-emitting layer; 9] The electron transport layer and/or electron injection layer of the electronic material. [11] The organic electroluminescent device according to [10] above, wherein

At least one of the electron transporting layer and the electron injecting layer further comprises a compound selected from the group consisting of a quinone-based metal complex, a derivative, a t-derivative, a quinone derivative, a derivative, and a benzopyrene [12] The organic electroluminescent device of the above [11], wherein at least one of the electron transport layer and the electron injecting layer further comprises a metal selected from the group Earth metal, rare earth metal, metal oxide, gold halide, alkaline earth metal oxide, alkaline earth metal halide, rare earth metal oxide, rare earth metal tooth, alkali metal organic complex,

At least one of an organic complex of an alkaline earth metal and an organic complex σ of a rare earth metal, a group. The organic electroluminescent device according to any one of the above [1] to [12]. A illuminating device having a ^(1)~ as described above. The organic electroluminescent device of the item. [Effect of the Invention] According to a preferred aspect of the present invention, it is possible to obtain, in particular, a light-emitting element

S 12 201224109 38673pif An organic electroluminescence element excellent in life. Further, according to another preferred aspect of the present invention, an organic electroluminescence device which is excellent not only in achieving excellent element life but also in balance with a driving voltage can be obtained. Moreover, the preferred electron transporting material of the present invention is particularly suitable for blue light emitting elements, by which a blue light emitting element having an element life comparable to a red or green light emitting element can be fabricated. In addition, by using the organic electricity

By exciting the optical element, a high-performance display device such as a full-color display can be obtained. [Embodiment] 1. The present invention represented by the formula (1) [C] u card β-compound compound The benzo[c]carbazole compound having a pyridine-containing substituent of the present invention will be described in detail. The benzo[Z]carbazole compound of the present invention is a compound represented by the following formula (1). Further, in the R, A & A, which constitutes the benzene of the compound represented by the formula (1), and R, A & A, which is substituted, may be substituted by hydrazine. [Chem. 11] \J/ /(\ (Α-3) (Α-4) -0 (A-1) (A-2)

A' wherein R in the formula (1) is an aryl group having a carbon number of 6 to 24 or a carbon number of 2 201224109. ^ου/jpif. The private owner and any of A and A in the formula (1) are selected from the group represented by the above formula (A-1), the group represented by the above formula (A.2), and the formula (4)). And one of the groups consisting of the groups represented by the above formula (A_4), and the other is an aryl group having a carbon number of 6 to 18. That is, either A or A, "an aryl group having a carbon number of 6 to 18".

Further, in the group represented by the above formula (4)) to the formula (earth A"_4), the bond to be bonded to _ is bonded to any carbon atom constituting the ring, but not two bonds are bonded to the same carbon atom. In the group represented by the formula (Α·4), the two rings of the condensation of the bond between the ring of the ring and the ring of the naphthalene ring and the ring of the naphthalene ring are indicated, and the carbon of the naphthalene ring is in addition to the bond with the benzo ring. Atomic carbon atoms are linked. And, the ring contained in the structures of R, A and A' may be substituted by an alkyl group having a carbon number of i 6 , a hexyl group or a phenyl group. An alkyl group having a carbon number of 1 to 6 may be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl isobutyl group, a butyl group, a t-butyl group, a n-pentyl group, an isopentyl group, Neopentyl, third

Di-n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-didecylbutyl, yl-based, and the like. Among the alkyl groups, as the substituent on the structure 3 of R, A and A, a mercapto group, an isopropyl group or a tributyl group is preferred, and a third butyl group is preferred. The number of the substituents is, for example, the largest substitutable, preferably one to three, more preferably one to two, and even more preferably one. As the "aryl group having 6 to 24 carbon atoms" in R, an aryl group having a carbon number of ',, and 6 to 16 is preferable, and an aryl group having a carbon number of 6 to 12 is more preferable.

14 S 201224109 38673pif The "aryl group" of the body can be exemplified by a phenyl group as a monocyclic aryl group and a (2-, 3-, 4-) biphenyl group as a bicyclic aryl group as a condensed bicyclic system. (1-,2-)naphthyl of aryl, as a triphenyl aryl group of triphenyl (cross-linked tris, bis bis-triphenyl-4,-yl, meta-triphenyl-5, - group, ortho-three stupid _3, · group, ortho-triphenyl- 4,-yl, p-triphenyl-2,-yl, m-triphenyl-2-yl, m-triphenyl-3-yl, Cross-linked triphenyl _4_yl, ortho-triphenyl-2-yl, ortho-triphenyl--, ortho-triphenylene; phenyl, p-triphenyl-2-yl, p-triphenyl-t-butyl, p-three · 4-yl) 'as a condensed tricyclic aryl group 3] 4, 9^, 1^1·, 2^]1·, 2, 3·, 4·, 9·)^, — : Tetraphenylene (5,_phenyl-m-triphenyl-2-yl, 5,·styl-inter):--3-yl, 5'-styl-dis-triphenyl-4-yl, Co-triphenyl-aryl-triphenyl-(1-,2.)------------------------------------------------------------------------- - '60 base and so on. Further, examples of the condensed ring-based aryl group may be mentioned. The number of substituents is, for example, a maximum of = = 1. The silk scarf is preferably a phenyl group, a group, a group: ί group, a group, a group, and a naphthalene scale. ^本本为=之^ Particularly preferred is a carbon number ^~ base 10 == carbon and a number of 2 to 15 heteroaryl groups, including ^ in addition to carbon. "Milk" can be used as a constituent ring For example, the hetero atom of oxygen and sulfur is exemplified by phenyl group, ke group, m, and iso. 201224109 580/Jpif ° 坐 坐 、 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° , e-disodium, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, ° thiol, dioxin, phenyl, isomeric, lH-η Wowyl, benzimidazolyl, stupid and oxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinalhenyl, isoquinolinyl, porphyrinyl, quinazolinyl, quinoxalinyl, Anthracenyl, naphthyridinyl, fluorenyl, acridinyl, oxazolyl, acridinyl, phenoxazinyl, phenothiazine, cyanoazinyl, pyridazinyl, furazyl, benzofuran; Base: isobenzofuranyl, benzo[b]thienyl, morpholyl, thiol and the like: preferred among these groups are pyridyl, quinolyl and isoquinolyl groups. ^1 As R, it is particularly preferable to enumerate the base represented by the following formula (R-1) to formula (汉_2〇). Further, the base is preferably a group represented by the following formula (Rq) to formula (R_14), more preferably a group represented by the following formula (u) to formula (RU), and further preferably further. It is a group represented by the following formula (R-1), formula (R_1〇), and formula (R-11). [化 12]

S 16 201224109 38673pif

(R-1)

(R-10)

(R·11) (R-12) (R-13)

(R-14)

(R-15)

(R·16) (R-17) (R-18)

(R-19)

(R-20)

The group represented by the above formula (A-1) selected as A or A' may be a 2-pyridyl group, a 3-pyridyl group or a 4-pyridyl group. The base represented by the above formula (A_2) selected by the vapor as A or A' can be listed as ^, 2'2-to-degree ratio _(3»,6-) base, 2,3,-to-degree ratio D-(3-,4-,5-,6-)-based, '4-to-bit ratio bite. (3.,4-,5-,6-) group, 3,2,-linked η ratio bite-( 2-,4·,5-,6-) base, 3,3'_ ^ 疋(2 ,4-,5-,6-) base, 3,4' ratio bite _(2_,4_,5_, 6_)yl, 4,2,-linked 2°M2-,3-,5-,6-)yl, 4,3'-bipyridyl-(2_,3-,5-,6-)yl, 4, 4,-bipyridyl_(2-,3-,5-,6-) group. , as A or A, and the selected formula (A_3) is represented by the above-mentioned formula (A_3). 201224109 38673pif 举.^ ratio °~2-yl)phenyl-2-yl decyl-3-yl)phenyl -2-yl-tertiarydinyl)phenylphenyl, (pyridin-2-yl)phenyl-3-yl, (pyridine-3-yl)phenyl-3_f-pyridyl)phenyl-3-yl, Pyridin-2-yl)phenyl-4-yl, (pyridine-3-yl)phenyl-4-yl, (n-bito-4-yl)phenyl-4-yl. As A or A, the base represented by the above formula (A_4) is selected (2 to 0), '; '4-, 5, 6-, 7-, 8-), 1_(4_pyridine ) / than 0 疋) C-(1,3-, 4_, 5, 6, 7-, 8_), 2<3-indenyl)naphthyl. ','5,6,7·,8-) base, 2-(4·° ratio) naphthalene-(1-,3-,4-,5-,6-,7-,8-) As a sputum or sputum, the "retrospective A t δ ^ ^ is preferably a square with a carbon number Μ u Γ and an inverse of 6 to 18", Fang Mei. Your U~r is a square of ～4. More preferably, the carbon number is 6 to 10, and the aryl group having a carbon number of 6 to 24 is listed in the above R. Limited to a base with a carbon number of 18 or less). Preferably, 'A or A' is: hydrogen, the following formula (A-1-1), Ϊ = the base of the formula, the following formula (Α·2_1)~—) τ; ΙΓλ^ 〜: (Α5 11) The base represented by ί(Α_4-6) and the base represented by the following formula (AH) Λ (A 5 11). [化13] 201224109 38673pif

Or && (A-1-1) (A-1-2) (A-1-3)

(A-2-13) (A-2-14) (A-2-1) (A-2-2) (A-2-7)

(A-2-6)

(A-2-15) (A-2-16) (A-3-1) (A-3-2) (A-3-3) (A-3-4) (A-3-5)

(A-2-17) (A-2-18) (A-2-12)

(A-3-6)

N (A-4-1) (A-4-2) (A-4-3) (A-4-4) (A-4-5) (A-4-6)

Or QrQr

(A-5-1) (A-5-2) (A-5-3) (A-5-4) (A-5-5) (A-5-6)

(A-5-7) (A-5-8) (A-5-9) (A-5-10) (A-5-11) Select the base represented by the above formula (A-5) as A or In the case of A', the group represented by the above formula (A-5-1) to formula (A-5-11) is more preferably the above formula (A-5-1) or the above formula (A-5-). 8) The formula represented by the formula (A-5-10) 19 201224109 38673pif is more preferably a base represented by the above formula (AH), the above formula (A-5_8) or the formula (A-5-9). Further, the base represented by the above formula (4)) to formula (A_4) is selected as the base of A or A, and the base represented by the above formula (A-1) to formula (A_4) is more preferably the above formula (4). - a group represented by the formula (4)_3), a group represented by the above formula (Α-2-1) to the formula (Α_2·18), and the above formula (Α-3-1) to (α-3-6) The base represented by the formula and the formula (A_4_i) to (A-4-3). Further, 'further better basis is the above-mentioned formula (A-Μ)~式(Α-υ) · the base represented by the above formula (Α_2_υ~式(Α_2_4), the above formula (Α-2-7) a group represented by the formula (Α-2-9), a group represented by the above formula (Α212), a group represented by the above formula (Α_2_15), and a formula represented by the above formula (AH) to (Α_3·6). And a group represented by the above formula (Α-4-1) to (Α_4_3). Further, a particularly preferred group is a group represented by the above formula (A-Μ)~式(Α小3;), and the above formula The base represented by (Α-2-1), the base represented by the above formula (Α_2_2), the base represented by the above formula (Α_2·7) to the formula (Α_2_9), and the above formula (Α-2-12) The base of the expression, the base represented by the above formula (8_3_1;)~ formula (Α3_6), and the base represented by the above formula (Α_4_υ~式(Α·4_3). Moreover, the most preferable base is the above formula (Α -1-2) the base represented by the above formula, the formula represented by the above formula (Α-2-2), the above formula (Α_2_7) to the formula (the base represented by α_州, the above formula (Α_3_υ~式(Α_3·6) The basis of the above. The above is taken as a Α or Α, and the preferred base is exemplified in R Phenyl is most suitable when the case or naphthyl.

S 20 201224109 38673pif Specific examples of the compound represented by the above formula (1) include, for example, the compounds represented by the following formulas (Μ) to (1-1398). Further, the numbering of the compounds exemplified below does not correspond to the number of the compound used in the scope of the patent application or the examples. The compound of the formula (1-335) used in the scope of the patent application or the examples corresponds to the compound of the formula (1-287) exemplified below, and likewise the compound of the formula (1-140) and the formula (1-106) Corresponding to the compound, the compound of the formula (1-212) corresponds to the compound of the formula (I. 72), and the compound of the formula (1-431) corresponds to the compound of the formula (1-375), and the compound of the formula (1-383) Corresponding to the compound of the formula (1-331), the compound of the formula (1-384) corresponds to the compound of the formula (1-332), and the compound of the formula (1-376) corresponds to the compound of the formula (1-324). The compound of (1_36〇) corresponds to the compound of the formula (1-310), the compound of the formula (1-408) corresponds to the compound of the formula (1-354), and the compound of the formula (丨_237) and the formula (1-195) Corresponding to the compound, the compound of the formula (Μ89) corresponds to the compound of the formula (Μ51), the compound of the formula (1-455) corresponds to the compound of the formula (1-397) and the compound of the formula (1-59) and the formula (丨-29) The compound corresponds to 0 [Chemical 14]

21 S 201224109 38673pif

[Chem. 15] 22 s 201224109 38673pif

(1-19) 9

(1-22)

(1-25) 9

(1-28)

(1-34)

(1-23)

(1-29)

(1-21)

(1-27)

(1-35)

(1-36) [Chem. 16] 23 201224109 38673pif

(1-40)

(1-42)

9

(1-44)

(1-45)

[Π化] 24 s 201224109 38673pif

9

(1-55) 9 9

(1-56)

(1-57)

(1-61)

(1-62)

(1-63)

[化 18] 25 201224109f

^\j\j t iJlI

9

(1-76)

(1-77)

P

(1-78)

(1-79)

(1-80)

(1-84)

[Chem. 19] s 26 201224109 38673pif

(1-94) (1-95)

(1-96)

(1-99)

[化 20] 27 9 201224109 38673pif

(1-109)

(1-110)

(1-111)

(1-121) (1-122) (1-123)

(1-124)

[化 21] 28 201224109 38673pif

[化 22] 29 201224109 3»0/3pif

(1-145)

(1-146)

(1-147) 9 N:

(1-148)

(1-149) 9

(1-150) 9

(1-151)

(1-152)

(1-153)

(1-154)

(1-155)

(1-156)

(1-157)

(1-158)

(1-159)

(1-160)

(1-161)

[Chem. 23] 30 201224109 38673pif

(1-163)

(1-164)

(1-165)

[Chem. 24] 31 201224109 38673pif

[化25] s 201224109 38673pif

[t. 26] t 33 201224109 38673pif

(1-232)

[化 27] 34 201224109 38673pif

(1-235)

(1-244)

(1-250)

(1*236)

(1-237)

(1-239) (1-240) 9

(1-242)

(1-243)

(1-245)

(1-246)

(1-251) (1-252) [Chem. 28] s 35 201224109 38673pif

(1-253) (1-254) (1-255)

(1-268) (1-269)

(1-270) [Chem. 29] s 36 201224109 38673pif

(1-274) (1-275) (1-276)

(1-277) (1-278) (1-279)

(1-280) (1-281) (1-282)

(1-286) (1-287) (1-288) [Chem. 30] 37 201224109 38673pif

(1-289) 9

(1-290)

(1-291)

(1-298) (1-299) (1-300)

(1-301) (1-302) (1-303)

[化31] 38 s 9 201224109 38673pif

(1-307) 9

(1-310)

(1-313)

(1-311)

(1-314) (1-315)

(1-318)

[化32] 201224109 i80/ipif

(1-331) (1-332) (1-333)

(1-342) [Chem. 33] s 40 201224109 38673pif

9

(1-346)

9 π

(1-352)

(1-355)

(1-358)

[化 34] 41 201224109, «·/ U V/,

(1-367)

(1-368)

(1-369)

(1-370)

(1-371)

[化35] 42 201224109 38673pif

(1-379)

(1-396) [Chem. 36] n:: 43 201224109

(1-406) (1-407) (1-408)

(1-409)

(1-410) (1-411)

(1-412)

(1-413)

(1-414) [Chem. 37] 44 201224109 38673pif

(1-418)

(1-419)

(1-420)

(1-422) (1-423)

(1-432) [化38] l|:: 45 201224109 38673pif

(1-433) 9

(1-434)

(1-435)

(1-442) (1-443) (1-444)

(1-445)

(1-446) (1-447)

[化39] 46 s 201224109 38673pif

9 9

(1-451) (1-452)

(1-453)

(1-463) (1-464) (1-465)

(1-466) [Chem. 40] 47 201224109 38673pif

(1-467) (1-468) (1-469) ^ ^ c?

(1-476) Eve C?

(1-477) (1-478)

(1-479)

(1-480)

(1-481)

[化41] s 48 201224109 38673pif

(1-485)

(1-488)

(1-486) (1-487)

(1-489) (1-490)

(1-494)

[化42] 49 201224109 38673pif

(1-504)

(1-506)

(1-507) (1-508)

(1-515)

(1-516)

(1-517)

(1-518)

[化43] s 50 201224109 / jpif

(1-521)

(1-523)

(1-524)

(1-527) (1-528)

(1-533) (1-534)

[化 44] 51 201224109 38673pif

(1-539) (1-540)

(1-542)

(1-544)

(1-545)

(1-548) (1-549)

(1-550)

(1-551) (1-552)

(1-553)

[化 45] 52

S 20122410938673pif

(1-560) (1-561) (1-562)

(1-564) (1-563)

(1-572)

C?

(1-574) [Chem. 46]

t 53 201224109 C?

(1-575) (1-576)

(1-577)

(1-583)

(1-584)

(1-587) (1-588)

(1-589)

(1-591)

(1-592) [Chem. 47] 201224109 38673pif

(1-593)

(1-594)

(1-595)

(1-605)

(1-606)

[化48]

S 55. 201224109 38673pif

[化49] s 56 201224109 38673pif

[化 50] 57 201224109 38673pif

[化 51] 58 s 201224109 38673pif

[化 52] 59 201224109 38673pif

(1-698)

(1-699) (1-700) [Chem. 53] 60 s 201224109 38673pif

(1-704)

(1-705)

(1-706)

(1-710) (1-711) (1-712) (1-713)

(1-716)

(1-718) [Chem. 54] 61 201224109 38673pif

(1-719)

(1-720) (1-721)

[化 55] 62 s 201224109 38673pif

(1-740) (1-741)

(1-742)

C?

(1-743) (1-744) (1-745)

(1-746) (1-747)

(1-748)

(1-752) (1-753)

(1-754) [Chem. 56] 63 201224109 38673pif

(1-755)

(1-756) (1-757)

(1-758)

(1-759)

(1-762) (1-763)

[化57] 64 s 201224109 38673pif C? (?

(1-773) (1-774) (1-775)

(1-777)

(1-778)

(1-779) (1-780) (1-781)

^

(1-785) (1-786) (1-787)

[化58] 65 201224103⁄4

(1-797) (1-798) (1-799)

[化59] s 66 201224109 38673pif

[化60] 67 201224109 38673pif

[化61] 68 s 201224109 38673pif

[化 62] 69 201224109 38673pif

CP

(1-875)

(1-877)

(1-880) (1-879) [Chem. 63]

S 70 20122410938673pif

(1-885)

(1-886)

(1-887)

(1-888) (1-889)

(1-898) (1-896) (1-897) [Chem. 64] 71 201224109 j«o/^pif

(1-899) (1-900) (1-901)

(1-902)

n eve (1-905) (1-906)

(1-907)

(1-911) (1-912) (1-913)

[化65] s 72 201224109 38673pif

(1-920) (1-921)

(1-923) (1-924)

(1-929)

(1-930)

(1-922)

(1-925)

(1-928)

(1-932) [Chem. 66] 73 201224109 3«673pif

(1-933) (1-934) (1-935)

[化67] s 74 201224109 38673pif

Σο

(1-954)

9〇

(1-961) (1-962)

[化68] 75 201224109 38673pif

Σο

(1-981)

[化69] 76 s 90 201224109 38673pif

(1-987)

(1-988)

Σο

(1-992)

(1-999)

(1-1000)

(1-1003)

[化70] ti:· 77 201224109 i86/3pif

Hb 71] 78 s 201224109 38673pif

Σο

(1-1028)

Qo

(1-1038)

[化72] ,,,· 79 201224109 38673pif

[化73] 80 s 201224109 38673pif

[化74] 81 201224109 38673pif

(1-1083)

[化 75] 82 s 201224109 38673pif

[化76] 83 201224109 38673pif

[化77] s 84 201224109 38673pif

[化78] 丨1:: 85 201224109 . ____ _ Γ1Ι

[化79]

s 86 201224109 38673pif

[化80] 87 201224109 38673pif

[化81] 88 s 201224109 38673pif

[化82] 89 201224109 38673pif

(1-1234) 90

(1-1235)

[化83] s 201224109 J)OU / jpif

9〇

(1-1253)

[化84] 91 201224109 38673pif

[化85] 92 s 201224109 38673pif

[化86]

93 S 201224109)if

[化87] s 94 201224109 38673pif

[化88] 95 201224109 joo/jpif

[化89]

vS 96 201224109 38673pif

[化90] 97 201224109 38673pif

90

(1-1368)

(1-1370) 90 ςο (1-1371) (1-1372)

90

(1-1375)

(1-1376)

(1-1382) [Chem. 91] s 98 201224109 38673pif

(1-1383) (1-1384) (1-1385)

(1-1388)

(1-1395)

(1-1398) With respect to the compound represented by the above formula (1-1) to formula (1-1398), among these compounds, in particular, the formula (1-1), the formula (1-9) to the formula (1-11) ), Equation 99 201224109 38673pif (1-19), Formula (1-20), Formula (1-22)~Formula (1-44), Formula (1-51), Formula (1-52), Formula (1) -55), Formula (1-62), Formula (1-63), Formula (1-66), Formula (1-73), Formula (1-74), Formula (1-77), Formula (1- 84), formula (1-85), formula (1-88) to formula (1-108), formula (1-110), formula (1-117), formula (1-118), formula (1-121) ), Formula (1-128), Formula (1-129), Formula (1-132) to Formula (1-198), Formula (1-205), Formula (1-206), Formula (1-209) , formula (1-216), formula (1-217), formula (1-269)~form (1-401), formula (1-408), formula (1-409), formula (1-419), Formula (1-420), Formula (1-423), Formula (1-430), Formula (1-431), Formula (1-434), Formula (1-441), Formula (1-442), Formula (1-445), formula (1-452), formula (1-453), formula (1-456), formula (1-463), formula (1-464), formula (1-467), formula ( 1-475), formula (1-476), formula (1-477), formula (1-485), formula (1-486), formula (1-488), formula (1-495), (1-496), formula (1-506), formula (1-507), formula (1-510), formula (1-517), formula (1-518), formula (1-521), formula ( 1-528), formula (1-529), formula (1-532), formula (1-539), formula (1-540), formula (1-543), formula (1-550), formula (1) -551), formula (1-554), formula (1-561), formula (1-562), formula (1-565), formula (1-572), formula (1-573), formula (1- 576), Formula (1-586), Formula (1-587), Formula (1-594), Formula (1-595), Formula (1-598), Formula (1-605), Formula (1-606) ), formula (1-609), formula (1-616), formula (1-617), formula (1-620), formula (1-627), formula (1-628), formula (1-631) , formula (1-638), formula (1-639), formula (1-642), formula (1-649), formula (1-650), formula (1-653), formula (1-660), Formula (1-661), formula (1-664), formula (1-671), formula (1-672), formula (1-675), formula (1-682), formula (1-683), formula (1-735), formula (1-742), formula (1-743), formula (1-746), formula (1-753), formula (1-754), formula (1-757), formula ( 1-764), formula (1-765), formula (1-768), formula (1-775), formula (1-776),

100 S 201224109 ^ου/jpif Formula (1-779), Formula (1-786), Formula (1-787), Formula (1-790), Formula (1-797), Formula (1-798), (1-801), formula (1-808), formula (1-809), formula (1-812), formula (1_819), formula (1-820), formula (1-823), formula (1- 830), formula (1-831), formula (1-834), formula (1-841), formula (1-842), formula (1-845), formula (1-852), formula (1-853) ), formula (1-856), formula (1-863), formula (1-864), formula (1-867),

Formula (1-874), formula (1-875), formula (1-878), formula (1-885), formula (1-886), formula (1-896), formula (1-897), formula (1-900), formula (1-907), formula (1-908), formula (1-911), formula (1-918), formula (1-919), formula (1-922), formula ( 1-929), Formula (1-930), Formula (1_933), Formula (1-941), Formula (1-942), Formula (1-951), Formula (1-952), Formula (1-954) ), formula (1-961), formula (1-962), formula (1-965), formula (1-972), formula (1-973), formula (1-976), formula (1-983) , formula (1-984), formula (1-987), formula (1-994), formula (1-995), formula (1-998), formula (1-1005), formula (1-1006), Formula (1-1009), Formula (1_1016), Formula (1-1017), Formula (1-1020), Formula (1_1〇27), Formula (1_1〇28), Formula (1-1031), Formula (1) -1038), Formula (1-1039), Formula (1-1042) ' Formula (1-1049), Formula (1-1050), Formula (1_1053), Formula (1_1〇6〇), Formula (1-1061) ), formula (1-1064), formula (1 - 1071), formula (ΐ_ι〇72), formula (1-1075), formula (1-1〇82), formula (ι·ι〇83), formula ( ι·1086), formula (1-1093), formula (1-1〇94), formula (1_1〇97), formula (2- ^04), Formula (1-1105), Formula (1-11〇8), Formula (Μ115), Formula (1-1116), Formula (1-1119), Formula (1_1126), Formula (Μ127), Formula (1_113〇), Formula (1-1137), Formula (1.1138), Formula d-nu), Formula (11148), Formula (1-1149), Formula (1_12〇1), Formula (1_12〇8), Formula (112〇9), Formula (1-1212), Formula (M219), Formula (M22〇), Formula (ii223), Formula!; 101 201224109 38673pif (1-1230), Formula (1-1242), Formula ( 1-1263), Formula (1-1275), Formula (1-1289), Formula (1-1308), Formula (1-1322), Formula (1-1340), Formula (1.1352), Formula (1) -1231), formula (1-1252), formula (Μ264), formula (1-1278), formula (Μ296), formula (Μ311), formula (1-1329), formula (1-1341), formula (1 -1355), formula (1-1234), formula (1-1253), formula (1-1267), formula (1-1285), formula (1-1297), formula (1-1318), formula (1- 1330), Formula (1-1344), Formula (1-1362), Formula (1-1241), Formula (1-1256), Formula (1-1274), Formula (1-1286), Formula (1-1300) ), formula (1-1319), formula (Μ333), formula (1-1351), formula (1-1363),

Compounds represented by (1-1366), formula (1_1373), formula (1-1374), formula (1-1377), formula (1-1384), formula (1·Π85), and formula (1-1388) good. Moreover, more preferred are formula (1_9), formula (1-10), formula (1-19), formula (1-20), formula (1-29), formula (1-30), formula (1- 40), formula (1-41), formula (1-51), formula (1-52), formula (1-62), formula (1-63), formula (1-73), formula (1-74) ), formula (1-84), formula (1-85), formula (1-95), formula (1-96),

Formula (1-106), Formula (1-1〇7), Formula (1-117), Formula (1-118), Formula (1-128), Formula (1-129), Formula (Μ39), Formula (1-140), Formula (1-150), Formula (1-151), Formula (1-161), Formula (1-162), Formula (1-172), Formula (1-173), Formula ( 1-183), Formula (1-184), Formula (1-194), Formula (1-195), Formula (1-276), Formula (1-277), Formula (1-287), Formula (1) -288), formula (1-298), formula (1-299), formula (1-309), formula (1-310), formula (1-320), formula (1-321), formula (1- 324), formula (1-331), formula (1-332), formula (1-342), formula (1-343), formula (1-353), formula (1-354), formula (1-364) ), Formula (1-365), Formula (1-375), Formula (1-376), Formula (1-386), Formula (1-387), Formula (1-397), Formula (1-398) , formula (1-408), formula (1-409),

102 S 201224109 38673pif Formula (1-419), Formula (1-420), Formula (1-43〇), Formula (ι_43ΐ), Formula (Μ"), Formula (1-442), Formula (i_452), Formula (1-453), a compound represented by the formula (1-463) and the formula (1-464). Further, particularly preferred are the formula (1-29), the formula (1-106), the formula (1_151), the formula (1_172), the formula (1_195), the formula (1-287), and the formula (1-31〇). a compound represented by the formula (1_324), the formula (1-331), the formula (1-332), the formula (1-354), the formula (1_375), and the formula (1_397). 2. Process for producing benzo[c]carbazole compound represented by formula (1) # Next' The method for producing the compound of the present invention will be described. The compound of the present invention can be basically a known compound, and a known synthesis method such as Suzuki coupling reaction or root-shore coupling reaction (for example, Metal-Catalyzed Cross-Coupling Reactions - Second,

Completely Revised and Enlarged Edition, etc., are synthesized and synthesized. Further, the two reactions can be combined to carry out the synthesis. The procedure for synthesizing the compound represented by the formula (1) by a Suzuki coupling reaction or a root-shore coupling reaction is exemplified as follows. Φ <Production method of the compound represented by the formula (1) (Part 1)><Synthesis of a pyridine group having a phenyl group or a naphthyl group having a reactive substituent> σ First, by the following The reaction formula (1) is synthesized to determine the vaporization of zinc, and then the zinc hydride complex of pyridine and 1,4-dibromobenzene or ι,4-di are obtained by the following reaction formula (2). The bromon naphthalene reaction can be used to synthesize 2-(4-bromopyridylpyridinyl or 2-(4-bromonaphthalen-1-yl)pyridine. [Chem. 92] !; 103 201224109 J5〇/jpif Reaction formula (1) Br seven

1) RLi or Mg or RMgX

2>ZnCI2 or ZnCI2· TMEDA

Znci_{3 reaction formula (2) Znd-〇

Br

Further, "ZnCl2 · TMEDA" in the reaction formula (1) is a tetramethylethylenediamine complex of zinc vapor. In "RLi" or "RMgX" in the above reaction formula (1), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3~ a branched alkyl group of 4, and X is a halogen. Here, a method of synthesizing 2-(4-bromophenyl)pyridine and 2-(4-bromonaphthalen-1-yl)pyridine using 2-bromopyridine as a raw material is exemplified, and 3-bromopyridine or 4- can also be used. Bromopyridine is used as a raw material, and iodide is used instead of bromide, thereby obtaining a corresponding target, namely 3-(4-bromophenyl)pyridine, 4-(4-bromophenyl)pyridinium, 3-(4-Bromonaphthalen-1-yl)acridine and 4-(4-bromonaphthalen-1-yl)pyridinium. Moreover, the synthesis of 2-(4-bromophenyl)pyridine and 2-(4. bromonaphthalen-1-yl)pyridine using 1,4-dibromobenzene or 1,4-dibromonaphthalene as raw materials is exemplified herein. As a method, 1,3-dibromobenzene, 2,6-dibromonaphthalene or 2,7-dibromonaphthalene can also be used as

S 104 201224109 38673pif f material 'different use of dichlorite < diiodide, bis(trifluoromethanesulfonate) or these, heterozygous (for example, (four) ice moth benzene, etc.) instead of using two deserts Body: thereby obtaining the corresponding target, namely 2-(3-bromophenyl)pyridine, 2-(6-bromonaphthyl)pyridinium and 2-(7-bromonaphthalen-2-yl)acridine Wait.

Further, it is also possible to substitute 1,4-, dibromobenzene or the like by a coupling reaction of 1,4-dioxabenzene or the like with π-ratio sigma-based carboxylic acid or π-ratio σ. The above-mentioned target is obtained by a coupling reaction with the reaction of the gasified zinc complex. Further, by appropriately selecting a raw material, a raw material for synthesis of the compound of the present invention represented by the formula (1), that is, an acridine having a phenyl group or a naphthyl group having various reactive substituents, may be obtained. . <Synthesis of pyridyl-substituted phenyl/naphthylboronic acid and borate esters> Sword m can be converted as a sample of H(3), and the organic clock tester 2 (4-/odorophenyl) ° ratio °Definite or naphthalene small base) bite for bellowing, or = use magnesium or a reagent as a Grenner reagent and react with ore triacetate, ethyl acetate or triisopropyl vinegar, thereby synthesizing 40 bites _2· 基·_ and 4 仰定_2_基)Naphthalene|base vinegar. Further, the duty can be hydrolyzed by the reaction formula (4), whereby the ratio can be synthesized. Benzo) phenylboronic acid and 4 butyl base naphthalene small boric acids. 105 201224109 "Reaction formula (3) 1) RLi or Mg or RMgX ^ 〇r*

2) (RO)3B ^ ^~^^B, 0R_ R*=decyl, ethyl, isopropyl, etc. or reaction formula (4)

In "RLi" or "RMgX" in the above reaction formula (3), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 丨~4 or a carbon number of 3~ 4 branches of the base, X is a function. Further, as shown in the following reaction formula (5), 2-(4-bromophenylpyridinyl or 2-(4-bromonaphthalen-1-yl)pyridinyl may be chlorinated or used using an organolithium reagent. Magnesium or organomagnesium reagent as a Grignard reagent with bis(pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4,4,5,5-tetramethyl-l,3,2-dioxa-borolane) reaction, thereby synthesizing other 4-(pyridin-2-yl)phenylborate or 4-(pyridine-2) -yl)naphthalen-1-ylborate. Further, as shown in the following reaction formula, a palladium catalyst can be used to test 2-(4-bromophenyl)beta ratio or 2-(4-bromonaphthalene). -1-Gibidine is coupled with boranoic acid pinacol ester or 4,4,5,5-tetradecyl-indole, 3,2-dioxaborolan, thereby synthesizing the same 4_ (pyridine-2-yl)phenyl boron

106 S 201224109 38673pif acid ester or 4-(pyridin-2-yl)naphthalen-1-yl borate. [化94]

Reaction formula (5)

In the "RLi" or "RMgX" in the above reaction formula (5), R represents a linear or branched alkyl group, preferably a linear alkyl group having a carbon number of 1 to 4 or a carbon number of 3~ a branched alkyl group of 4, and X is a halogen. Further, in the above reaction formula (3), reaction formula (5) or reaction formula (6), the corresponding positional isomer may be used to synthesize the corresponding boric acid/borate ester: 3-(4) -Bromophenyl)pyridine, 4-(4-bromophenyl)pyridine, 2-(3-bromophenylbipyridine, 3-(3-bromophenyl)acridine, 4-(3-bromophenyl) ). 107 201224109 38673pif bite, 3-(4-naphthalene-l-yl). Bite, 4 (4 plays Cai Xiaoji). 唆-1-base) bite, 2♦ naphthalene_2_ base) Bite, 3_(6•漠蔡_2 base) 4-(6-molynaphthalene-2-yl wind bite, 2-(7·漠蔡_2 base) as set, 4-(7·演蔡_2 Qibi bite. 4#-2- Furthermore, in the above reaction formula (3), reaction formula (5) or reaction formula (6), it is also possible to use a vapor, moth or trifluoro acid as a substitute for An evolution of 4 bromophenyl)pyridine and 3·(4-bromonaphthalen-i-yl)pyridine, π _ synthesis. <Synthesis of bipyridine with reactive substituents> The reaction of the formula (7) to synthesize the zinc hydride of the pyridine is followed by the following reaction formula (8), the zinc pyridine of the pyridine is mixed with the 2,5·dibromopyridine to thereby synthesize 5- Bromine-2,2 - bipyridine 〃 [of 95] Reaction of formula (7)

ClZn

Reaction formula (8)

ClZn -ο 1) RLi or Mg or RMgX 2) ZnCI2 or ZnCI2.TMEDA Br

Pd-catalyst

Further, "ZnCl2·TMEDA" in the reaction formula (7) is a tetramethylethylenediamine complex of zinc chloride. In "RLi" or "RMgX" in the above reaction formula (7), R represents a linear or branched alkyl group, preferably carbon.

S 108 201224109 38673pif The number is a direct bond of 1~4 prime 0 or a branched alkyl group having a carbon number of 3 to 4, X is a halogenated acridine, and f is synthesized by using 2_bromopyridinium as a raw material. Bromine-2, material, and Hi can make 3 life ratio bite or 4♦ than bite as the original target object 1 === object 'by which respectively obtain ^ θ Wu, 3 to π 疋 or 5 - desert - 2,4,-bipyridine.

溟 疋 or 3,5-dibromopyridine as raw material = fluoromethyl 1_ or _ mixed into two: ^ that is 6, the emperor does not use H wrong to obtain the corresponding target, that is, 6 - desert -2 , 2, let pyridine, 4|2, 2, let pyridine and the like. Moreover, by making 2,5_2 deductive and biting the base acid or bite, the text is stored in the reverse coupling reaction to store the 2,5·κ read bite of the vaporized zinc. The coupling reaction of the reactants is carried out to obtain the above target.

Further, by appropriately selecting a raw material, a raw material for synthesis of the compound of the present invention represented by the formula (1), that is, a bipyridine having various reactive substituents can be obtained. ~ <Combination of α-α bite acid/sole vinegar> Next, as shown in the following reaction formula (9), the agent can be used for 5|2"b money or the secret or organic town can be used as The Grignard reagent is reacted with tridecyl succinate, triethyl borate or triisopropyl sulphate to synthesize 2,2'-bipyridyl borate. In addition, it can be - And the 2, 2, ♦ heart __ is hydrolyzed with straw 109 201224109 38673pif thereby synthesizing 2,2'-bipyridyl boric acid. [Chem. 96] Reaction formula (9) 〇-Λ^~ΒΓ

pR' B, OR' 1) RLi or Mg or RMgX ---1

2) (R'0)3B R'=decyl, ethyl, isopropyl, etc.

The reaction formula (10) Η+3〇CK><: ,€Κ><ηη is in the "RLi" or "RMgX" in the above reaction formula (9), and R represents a linear or branched alkyl group. 'It is preferably a linear alkyl group having a carbon number of 1 to 4 or a branched alkyl group having a carbon number of 3 to 4, and X is a halogen. Further, as shown in the following reaction formula (11), an organolithium 5 type agent can be used for 5-bromo-2,2'-linked. Lithium is pyridine, or magnesium or organomagnesium is used as a Grignard reagent with pinacol borate or 4,4,5,5-tetradecyl. ^3,2·dioxaborolane is reacted to synthesize other 2,2,-bipyridyl-borate. Further, as shown in the following reaction formula (12), 5-bromo-2,2,-bipyridyl and diboronic acid pinacol ester or tetramethyl-1,3,2- can be used using a catalyst and a base. The dioxolane borane is subjected to a coupling reaction, whereby the same 2,2,-bipyridyl borate is synthesized. [化97]

S 110 201224109 .

Reaction formula (11) €Η>βγ reaction formula (12) €K>r

1) RLi or Mg or RMgX

CK>b:^

Pd-catalyst/base €k>b: ^ In "RLi" or "RMgX" in the above reaction formula (11), R represents a linear or branched alkyl group, preferably a carbon number of 1~ a linear alkyl group of 4 or a branched alkyl group having a carbon number of 3 to 4, and X is a _ element. Further, in the above reaction formula (9), reaction formula (11) or reaction formula (12), 5-bromo-2,3'-bipyridine, 5-bromo-2,4-bipyridine, 5 may also be used. a positional isomer such as bromo-3,4'-bipyridine or 4-bromo-2,2'-bipyridine to synthesize the corresponding boric acid/borate. Further, in the above reaction formula (9), reaction formula (11) or reaction formula (12), a chloride, an iodide or a trifluoromethanesulfonate may be used instead of, for example, 5-bromo-2,2'-linkage. A bromide such as pyridine is synthesized in the same manner. <Synthesis of an aryl group having a reactive substituent and its boric acid/boric acid ester> Selecting an "aryl group having a carbon number of 6 to 18" (for example, formula (A-5-1) to 111 201224109 38673pif W In the case of A or A, in the case where the compound having a reactive substituent or a boronic acid/boronic acid ester thereof is commercially available, or the above-mentioned combination can be referred to And synthesis. <Synthesis of a central skeleton portion> First, as shown in the following reaction formula (13), 1-methoxy ice (4-decyloxy-2-phenylphenyl) is synthesized by a coupling reaction. Naphthalene. Here, Suzuki coupling using boric acid is exemplified in the reaction formula (13), but root-shore coupling using a rhythm compound may also be employed. Next, a cyclization reaction is carried out using triethyl phosphite or triphenyl scale to obtain a benzo[c]carbazole derivative (BCz-A).

The BCz-A is formed into BCz-B by a coupling reaction using a catalyst or a ullmann reaction, and then demethylated by boron tribromide or a pyridine salt or the like. Made into BCz-C. Thereafter, it is reacted with trifluoromethanesulfonic anhydride to obtain a central skeleton portion of the compound of the present invention: bis(trifluoromethanesulfonate) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester. [化98]

112 S 201224109 38673pif Reaction formula (Ί 3 )

The reaction of the third stage of human flight is to bond a reaction corresponding to the portion of r of the formula i1 represented by the formula (1) 'in the reaction, by using the corresponding soil or heteroaryl bromide or iodine Instead of bromobenzene or iodobenzene, the compound can be combined with an intermediate having different substituents on N. <Synthesis of the central skeleton portion.> Further, the central skeleton portion can be synthesized as follows. First, as shown in the following reaction formula (13), ^-(, 2-nitro-l,4-phenylene)bis(1-methoxynaphthalene) was synthesized by a coupling reaction. Here, in the reaction formula U'), the Suzuki coupling using boric acid is shown, and the root coupling using zinc is also used. Next, the benzo[c]carbazole derivative (BCz-A') is obtained by the use of sulfamic acid triethyl or triphenylphosphine to carry out a reaction. Thereafter, N-phenylation (BCz-B1) is carried out by the above method, followed by demethylation (BCz-C')', and finally reacted with trifluoromethanesulfonic anhydride to obtain the compound of the present invention 113 201224109 Central skeleton: 4-(7-phenyl-5(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]fluoren-9-yl)naphthalene-trifluorosulfonate- 1-yl ester. Reaction formula (1 3 ′)

N〇2 Br-〇^Br

BBr3 or PyHCI, etc.

<Synthesis of a diborate of a central skeleton portion> The bis(trifluoroanthracenesulfonic acid) obtained by the reaction formula (13) can be obtained by using a palladium catalyst and a base as shown in the following reaction formula (14). 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester with pinacol borate or 4,4,5,5-tetradecyl-1,3,2-dioxo The heterocyclic pentaborane is subjected to a coupling reaction, whereby 7-phenyl-7H-benzo[c]carbazole-5,9-diborate is synthesized. [化100] 201224109 38673pif Reaction formula (1 4 )

<Synthesis of diborate of the central skeleton portion. The trifluorosulfonium sulfonic acid 4 obtained by the reaction formula (13.) can be obtained by using a palladium catalyst and a base as shown in the following reaction formula (14'). -(7-phenyl-5(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]indazol-9-yl)naphthalen-1-yl ester and boronic acid pinacol Synthesis of 7-phenyl-5-(4,4,5,5 by ester or 4,4,5,5-tetradecyl-1,3,2-dioxaborolane -tetramethyl-1,3,2-dioxaborolan-2-yl)-9-(4-(4,4,5,5-tetradecyl-l,3,2-dioxo Heterocyclic borane-2-yl)naphthalene-l-yl)-7H-benzo[c]carbazole. [化101]

<Synthesis of the benzo[C]carbazole compound of the present invention by the Suzuki coupling reaction&gt; As shown in the following reaction formula (15), the above-mentioned double can be made under the reference of the catalyst and the test 115 201224109 38673pif Trifluoromethanesulfonic acid) 7-phenyl-7H_benzo[C]carbazole-5,9-monoester with 2 times molar π ratio biting benzoic acid or rancidate, σ ratio bite The benzo[c]carbazole compound of the present invention is synthesized by reacting a substituted phenyl/naphthyl boronic acid or a boric acid ester or a π-butanic acid or a boric acid ester. Here, 'exemplification is the use of 4-pyridylboronic acid/ benzoate, 4-indolyl-2-yl)phenyl rotten acid/borate, 4-(pyridin-2-yl)naphthalen-1-ylboronic acid /Borate ester and 2,2,-bipyridin-5-ylboronic acid/boronic acid ester synthesis method, but they can also be synthesized in the same manner using the respective positional isomers. Further, 4-(7-phenyl)-5(((difluoroindenyl) fluorenyl)oxy) benzo[c]咔nyl)naphthalen-1-yl trifluorosulfonate can also be used instead. The benzo[c]carbazole compound of the present invention is synthesized by bis(trifluorosulfonium sulfonic acid) 7-styl 7 Η 笨 and oxazol-5,9-diyl ester. Reaction formula (15) χ_η〇 or χΌ~0 or

In the above reaction formula (15), R represents a linear or branched alkyl group, preferably a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 3 to 4 carbon atoms. 116 201224109 38673pif Furthermore, 7-phenyl-7H-benzo[c]carbazole-5,9-diborate can be obtained in the presence of a catalyst base as shown in the following reaction formula (16). (4) with a 2-fold molar reactive substituent, a phenyl/naphthyl group with a reactive substituent or a reactive substituent. The benzo[c]carbazole compound of the present invention is synthesized by this reaction. The use of a 4-reactive group to replace hydrazine is exemplified herein. Determined, 2_(4_reactive substituted phenyl) bite, 2_(4_reactive substituted naphthalen-1-yl) D or pyridine or 5_reactive group substituted 2,2,·biacidine However, it is also possible to carry out the same synthesis using the respective positional isomers and also use 7-phenyl-5-(4,4,5,5-tetradecyl-1,3,2-diox Heterocyclic pentylene-2-yl)-9-(4-(4,4,5,5-tetradecyl-1,3,2-dioxaborolan-2-yl)naphthalene-1 - Synthesis of the benzo[c]u-salt compound of the present invention by substituting 7-7-benzo[c]carbazole in place of 7-phenyl-7Η-benzo[c]carbazole-5,9-lactamate . Reaction formula (1 6 ) or $

Further, as described in the following reaction formula (17), the above-mentioned bis(trifluorosulfonium sulfonate) 7-phenyl-7 Η 笨 并 (4) 咔嗤-5 may be obtained in the presence of a palladium catalyst and a base. 9-diester ester with 1 mole of pyridine boronic acid or borate, pyridine

117 S 201224109 38673pif Amidino-substituted naphthyl/naphthyl acid-depleted or boric acid vinegar or a combined D ratio. The intermediate (first stage) is synthesized by reacting benzene or boric acid ester, and further with 1 mol of pyridine boric acid or boric acid ester in the presence of a palladium catalyst and a base. The benzo[C]carbazole compound of the present invention is synthesized by reacting a boronic acid or a boronic acid ester of a phenyl/naphthyl group substituted with a phenyl/naphthyl group or a boronic acid ester of a bipyridyl acid to form a boronic acid ester (second stage). Further, phenyl-5(35((trifluoromethyl)sulfonyl)oxy)-7H-benzo[C]carbazole-9-yl)naphthalene-yl group can also be used. The benzo[〇] lysine compound of the present invention is synthesized instead of bis(trifluorosulfonium sulfonate) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester. [104]

118 S 201224109 38673pif

Reaction formula (1 7) or

X~0 or or or an arylboronic acid or an aryl boronic ester The compound of the present invention (second stage)

Pd-catalyst/alkali port/OH /OR / B, 〇H or or B,

0H OR V

In the reaction of the reaction formula (17), after the end of the first stage reaction, the purification operation may be carried out as needed. Further, it is also possible to use a boric acid or a boric acid ester of a pyridine which is different from the first stage, a boronic acid or a boronic acid ester of a phenyl/naphthyl group substituted with a pyridyl group or a boric acid or a boric acid ester of a bipyridine, respectively. A stupid [c]carbazole compound different in the substitution of the 5-position and the 9-position substituent is synthesized. In addition, an aryl boronic acid such as phenylboronic acid or naphthyl rotonic acid can be used in the first stage or the second stage, thereby synthesizing the benzene substituted by the aryl group at the 5- or 9-position of the oxazolyl group. [c] carbazole compound. The compound is equivalent to 119 201224109 38673pif A or A in the compound represented by the formula (1), and the "aryl group having a carbon number of 6 to 18" is selected (for example, the formula (A-5-1) to the formula (A-5) -11) a compound represented by the group). Similarly, 7-phenyl-7H-benzo[c]anthracene-5,9-diborate is reacted in the presence of a palladium catalyst and a base as shown in the above reaction formula (16). When the pyridine of the substituent or the phenyl/naphthyl group having a reactive substituent is reacted with a bite, the ratio of the phenyl/naphthyl group having a reactive substituent is bonded. The biting or the aryl group such as bromobenzene or bromonaphthalene is carried out in two stages, whereby the benzoquinone (4) taste of the present invention can be synthesized. Sit on the compound. Specific examples of the Ιε catalyst used in the eucalyptus coupling reaction include tetrakis(triphenylphosphine)palladium(0): Pd(PPh3)4, bis(triphenylphosphine)dichloropalladium (π): PdCl2 (PPh3) 2, Ig(II) acetate: Pd(OAc)2, tris(dibenzylidenepropene) dipalladium (0): Pd2(dba)3, tris(diphenylideneacetone)dipalladium (9) gas Folding complex: Pd2(dba)3 · CHC13, bis(dibenzylidenepropene), (9): Pd(dba)2, (l,l,-bis(diphenylphosphino)ferrocene) Palladium (II): Pd(dppf)Cl2, PdCl2{P(t-Bu)2-(p-NMe2-Ph)}2, bis(diphenylmethylene) and the like. Further, in order to promote the reaction, a phosphine compound may be added to the palladium compounds as the case may be. Specific examples of the phosphine compound include tris(t-butyl)phosphine, tricyclohexylphosphine, 1-(anthracene, fluorene dioxime)-2-(di-t-butylphosphino)-dimenole Iron, 1-(anthracene, fluorene-dibutylaminoindenyl)-2-(di-t-butylphosphino)ferrocene, 1-(decyloxymethyl)-2-(di-tertiary) Radyl, ferrocene, bis(di-t-butylphosphino)ferrocene, 2,2'-bis(di-t-butylphosphino)-!,! , _ binaphthyl, 2-decyloxy-2'-(di-t-butylphosphinyl binaphthyl, or 2-dicyclohexene 201224109 38673pifylphosphino-2',6'-dimethoxybiphenyl. Specific examples of the base to be used in the reaction include sodium carbonate, potassium carbonate, carbonic acid planer, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium butoxide, sodium acetate, and cans. Acidic, or potassium fluoride.

Further, specific examples of the solvent used in the reaction include benzene, toluene, dimethyl benzene, 1,2,4-trimethylbenzene, n,N-didecyl decylamine, tetrahydrofuran, diethyl ether, Tert-butyl mercaptoether, 丨'4·dioxane, decyl alcohol, ethanol, cyclopentyl decyl ether or isopropanol. These solvents may be appropriately selected and used singly or as a mixed solvent. &lt;Production Method of Compound represented by Formula (1) (Part 2)&gt; The above-described synthesis method of benzo coupling using the benzo[c]carbazole compound of the present invention can also be carried out by root-shore coupling. First, as shown in the following reaction formula (18), an organic agent is used for 4_pyridine, 4·(2_η-pyridyl)·!__ benzene, 4_(2_〇 口 定 base odor or 5-bromine -2,2'-bipyridine is lithiated, or magnesium or organomagnesium gas is used as a Grignard reagent and reacted with zinc vapor or zinc hydride tetramethylethylenediamine oxime = (ZnCl2 · TMEDA) Thereby synthesizing each zinc object 121 201224109 38673pif reaction formula (18) V^-Br

Br Br

1) RLi or Mg or RMgX -~~~^ 2) ZnCI2 or ZnCI2.TMEDA

Or CH&gt;

Br CK&gt;Zn〇.

Further, "ZnCl2 · TMEDA" in the reaction formula (18) is a gasified tetradecylethylenediamine complex. In the m" of the above reaction formula (18), R represents a linear mosquito, preferably a carbon &quot;, a linear alkyl group of ～4 or a branched alkyl group having a carbon number of 3 to 4. Further, it is also possible to carry out the same treatment using a telluride instead of the bromide. Here, 4·bromopyridine, 4—(2-pyridyl) small bromine, 4—(2_pyridylpyrene·naphthalene and the like) are exemplified. 5· _2, 2, _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Synthesis &gt; Finally, as shown in the following reaction formula )9), bis(trifluoromethanesulfonic acid) 7-phenyl·7Η_benzo[c]carbazole-5 can be used in the following = a 9-pyridyl zinc complex, a 4-(pyridin-2-yl)phenyl/naphthalen-1-yl zinc complex or a 2-fold molar synthesized as described above or The 2,2,-biindole _5-yl zinc scorpion sigma reaction, thereby synthesizing the benzo[c]thalthene compound of the present invention. Moreover, as shown in the following reaction formula (20), the

S 122 201224109 38673pif A zinc complex or a zinc complex of an aryl group such as a phenyl group or a naphthyl group is reacted in two stages in the same manner as in the above reaction formula (17) to synthesize the benzo[C] of the present invention. ] carbazole compound. Further, 4-(7-phenyl-5(((trifluoromethyl)sulfonyl)oxy)-7H-benzo[c]indazol-9-yl)naphthalene-trifluoromethanesulfonate can also be used. The benzo[c]carbazole compound of the present invention is synthesized by substituting 1-yl ester for bis(trifluorosulfonium sulfonate) 7-phenyl-7H-benzo[c]carbazole-5,9-diyl ester. [化106]

123 201224109 38673pif

Reaction formula (2 Ο ) or

Intermediate (Phase 1) /=Ν Ν=\

Or X X = ZnCI the compound of the invention -► (second stage)

Specific examples of the palladium catalyst used in the Pd-catalyst root-coupling reaction include tetrakis(triphenylphosphine)palladium(0): Pd(PPh3)4, bis(triphenylphosphine)digo palladium(II). : PdCl2(PPh3)2, palladium(II) acetate: Pd(OAc)2, tris(dibenzylideneacetone) dipalladium(0): Pd2(dba)3, tris(dibenzylideneacetone)dipalladium ( 0) Chloroform error

124 S 201224109 38673pif Compound: PdXdba)3 · CHCV Bis(dibenzylideneacetone) put (〇): pd(dba) 2, bis(dioxadiphenyl group)! Bar (0), or double ( Diphenylphosphino)-ferrocene) Digas Ib (II): Pd(dppf)Cl2. Further, specific examples of the solvent used in the reaction include benzene, toluene, diphenylbenzene, 1,2,4-trimercaptobenzene, N,N-didecylguanamine, tetrahydrofuran, diethyl ether, and Tributyl decyl ether, cyclopentyl decyl ether or hydrazine, 4 dioxin. Some solvents may be selected as appropriate, and may be used singly or as a mixed solvent. Further, the compound of the present invention also contains at least a part of hydrogen atoms which are substituted by hydrazine, and such a compound can be synthesized in the same manner as described above by using a raw material which is deuterated at a desired position. u 3. Organic electroluminescence element The benzo[c]carbazole compound having a pyridine-containing substituent of the present invention, for example, I is used as a material of an organic electroluminescence element. Hereinafter, the organic electroluminescent device of the present embodiment will be described in detail based on the drawings. Figure i is a schematic cross-sectional view showing an organic electroluminescent device of the present embodiment. &lt;Structure of Organic Electroluminescence Element&gt; The organic electroluminescence element 1 shown in Fig. 1 has a substrate 1A, an anode 102 provided on the substrate 101, and a hole injection layer provided on the anode 102. 103. A hole transport layer 1〇4 disposed on the hole injection layer 103, a light-emitting layer 1〇5 disposed on the hole transport layer 104, and an electron transport layer 106 disposed on the light-emitting layer 1〇5. The electron injection layer 1〇7 on the electron transport layer 1〇6 and the cathode 1〇8 provided on the electron injection layer 107. In addition, the organic electroluminescent device 100 may be reversed in the order of fabrication. For example, 125 201224109 38673pif is configured to have the following components: a substrate 1〇1, a cathode 108 disposed on the substrate 1〇1, and a cathode 1〇8. The electron injecting layer 1〇7, the electron transporting layer 1〇6 provided on the electron injecting layer 107, the emitting layer 105 provided on the electron transporting layer 1〇6, and the hole transporting layer provided on the light emitting layer 1〇5 1〇4, a hole injection layer 1〇3 provided on the hole transport layer 104, and an anode 102 provided on the hole injection layer 1〇3. It is not necessary to be the above layers, and the smallest constituent unit is composed of the anode 102, the light-emitting layer 105, the electron transport layer 1〇6, and/or the electron injection layer 1〇7, the cathode 108, the hole injection layer 1〇3, and the hole transport. Layer 1〇4 is a layer that can be arbitrarily set. Further, each of the above layers may be composed of a single layer or may be composed of a plurality of layers. As a state of the layer constituting the organic electroluminescence element, in addition to the above-described configuration of "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", It can also be: "substrate / anode / hole transport layer / light-emitting layer / electron transport layer / electron injection layer / cathode", "substrate / anode / hole injection layer / light-emitting layer / electron transport layer / electron injection layer / cathode "Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Injection Layer / Cathode", "Substrate / Anode / Hole Injection Layer / Hole Transport Layer / Light Emitting Layer / Electron Transport Layer / Cathode "Substrate / Anode / Light Emitting Layer / Electron Transport Layer / Electron Injection Layer / Cathode", "Substrate / Anode / Hole Transport Layer / Light Emitting Layer / Electron Injection Layer / Cathode", "Substrate / Anode / Hole Transport Layer" / luminescent layer / electron transport layer / cathode", "substrate / anode / hole injection layer / luminescent layer / electron injection layer / cathode", "substrate / anode / hole injection layer / luminescent layer / electron transport layer / cathode" , "Substrate / Anode / Light Emitting Layer / Electron Transport Layer / Cathode", "Substrate / Anode / Luminescence / 201224109 38673pif / cathode configuration aspects "of the electron injection layer. &lt;Substrate of Organic Electroluminescence Element&gt; The substrate 101 serves as a support for the organic electroluminescence element 100, and generally, quartz, glass, metal, plastic, or the like is used. The substrate 101 may be formed into a plate shape, a film shape or a sheet shape as needed, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet or the like can be used. Among them, preferred are glass plates, and transparent synthetic resin plates such as polyester, polydecyl acrylate, polycarbonate, and polysulfone. In the case of a glass substrate, soda lime glass or alkali-free glass or the like is used, and if the thickness is also a thickness sufficient to maintain mechanical strength, it is preferably 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. Regarding the material of the glass, it is preferable that the eluted ions from the glass are small, so that the alkali-free glass is preferable, but the limestone glass having a barrier coat such as Si〇2 is commercially available. Therefore, it can also be used. Further, on the substrate 1〇1, a gas barrier film such as a dense ruthenium oxide film may be provided on at least one surface in order to improve gas barrier properties, and in particular, a synthetic resin plate or film having low gas barrier properties. When a sheet is used as the substrate 101, it is preferable to provide a gas barrier film. &lt;Anode of Organic Electroluminescence Element&gt; The anode 102 functions to inject a hole into the light-emitting layer 105. In addition, when a hole injection |1〇3 and/or an electric/conveying layer 104 is provided between the anode 102 and the light-emitting layer 105, the layer 1〇3 and/or the hole are injected through the hole. The transmission layer 104 injects a hole into the light-emitting layer 1A5. Examples of the material forming the anode 102 include inorganic compounds and organic compounds. Examples of the inorganic compound include metal (Sau, Gold, Silver, Record, Saturated, 127 201224109 38673pif chromium, etc.), metal oxide (indium oxide, tin oxide, indium-tin oxide (ITO), indium- Oxide (IZO), etc., halogenated metal (such as copper iodide), copper sulfide, carbon black, ITO glass or Nesa glass. Examples of the organic compound include polythiophene such as poly(3-mercaptothiophene) and poly. Further, a conductive polymer such as a blister or a polyaniline may be appropriately selected and used from the material used as the anode of the organic electroluminescent device. The electric resistance of the transparent electrode is not particularly limited as long as it can supply a sufficient current to the light-emitting element, and it is preferable to reduce the electric resistance of the self-luminous element from the viewpoint of power consumption. For example, a substrate of 3 〇〇 ω / □ or less functions as an element electrode, and a substrate of about 1 〇 Ω / □ is now available. Therefore, for example, it is particularly preferable to use 100 Ω / □ 〜 5 Ω / □ Preferably, it is a low resistance product of 50 Ω/□ to 5 Ω/□. The thickness of ΙΤ0 can be selected according to the resistance value, and is usually used between 1 〇〇 nm and 300 nm. &lt;Cell injection layer and hole transport layer of organic electroluminescence element&gt; The hole injection layer 103 injects holes which are moved from the anode 1〇2 into the light-emitting layer 105 efficiently or in a hole. It is used in the transport layer 1〇4. The hole transport layer 104 functions to efficiently transfer the holes injected from the anode 102 or the holes injected from the anode 102 through the hole injection layer 1〇3 to the light-emitting layer 105. The hole injection layer 1〇3 and the hole transport layer 1〇4 are formed by laminating and mixing one or more types of holes and materials, or by injecting and transferring materials and holes. Formed from a mixture of molecular binding agents. Further, an inorganic salt such as ferric chloride (ΠΙ) may be added to the hole injection and transport material to form a layer. As a hole injection and a transporting substance, it is necessary to efficiently inject and transport a hole from the positive electrode between the electrodes for applying an electric field. Therefore, it is preferable that the hole injection efficiency is high, and the injected hole can be efficiently transmitted. . Therefore, it is preferable that the free potential (i〇nizati〇n p〇tential) is small, the hole mobility is large, and the stability is excellent, and it is difficult to produce impurities which are traps at the time of production and use. The material forming the hole injection layer 1〇3 and the hole transport layer 1〇4 can be used by selecting any compound from the following compounds: it has been conventionally used as a charge transport material for holes in photoconductive materials. The compound is a known compound used in a P-type semiconductor, a hole injection layer of an organic electroluminescence element, and a hole transport layer. Specific examples of such compounds are preferably 疋.β卡嗤竹生物 (n_phenyl leaf_sitting, polyethylene sitting, etc.), bis(ν·arylcarbazole) or bis(N-alkylcarbazole) a biscarbazole derivative triarylamine derivative (a polymer having an aromatic tertiary amino group in a main chain or a side chain), a bis-- φ di-p-phenylene phenyl phenyl) cyclohexane, N,N,-diphenylanthracene, Ν'-bis(3-mercaptophenyl)-4,4'-diaminobiphenyl, anthracene, Ν'_diphenyl Ν, Ν, _ Naphthyl_4,4,-diaminobiphenyl, anthracene, fluorene, -diphenyl-fluorene, anthracene, -bis(3-methylphenyl)_4,4,_diphenyl-1,1' Diamine, hydrazine, Ν'-dinaphthyl-hydrazine, hydrazine, -diphenyl _4,4,-diphenyl], γ-diamine, 4,4,,4',-three (3 a triphenylamine derivative such as a nonylphenyl (phenyl)amino)trisylamine, a starburstamine derivative, a derivative, a phthalocyanine derivative (no metal, copper phthalocyanine) And the like, a pyrroline derivative, a quinone compound 'benzofuran derivative or a thiophene derivative, an oxadiazole derivative, a heterocyclic compound such as a exoline derivative, a polydecane, etc. Preferred in the polymer system 129201224109 38673pif is a polycarbonate or a styrene derivative having a monomer in a side chain, an enezazole and a polydecane, etc., and is a film which can form a light-emitting element, and is transported from a 11⁄4 pole main hole and additionally transmitted. The compound of the hole is specifically limited. 1,... Moreover, it is also known that the conductivity of the organic semiconductor is strongly affected by the doping of A. The organic semiconductor matrix substance is composed of a compound having a good electron supply P or It is composed of a compound having good electron acceptability. In order to hold a supply of a substance, tetracyanoquinone dioxane (TCNQ) or 2,3 5 6 tetrafluorotetracyano-1,4-benzoquinone is known. Stronger electrons such as alkane (F4TCNq) (for example, Reference &amp; r M. Pfeiffer 5A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett. &gt; 73(22) 3 202-3204 ( 1998), n Seven 'Nine' and drama t "J_Bl〇ChWitZ, M.Pheiffer, T.Fritz, [Leo, Appl Phys 73 73 (6), 729-731 (1998)"). These compounds generate so-called holes due to electron transfer processes in electron-supplying type substrates (hole transport materials). The conductivity of the base material varies considerably due to the number of holes and the mobility. A matrix substance having a hole transporting property is known, for example, a benzidine derivative (TPD or the like) or a starburst amine derivative (TData, etc.), or a specific metal phthalocyanine (particularly zinc phthalocyanine ZnPc, etc.). [Patent No. 2005-167175]. &lt;Light-emitting layer of organic electroluminescence element&gt; The light-emitting layer 105 is a hole between the electrodes for imparting an electric field by injecting a hole from the anode 1〇2 and the self-cathode 1 〇8 injected electrons recombined to illuminate the layer. The material of the illuminating layer 105 is stimulated by the recombination of holes and electrons.

S 130 201224109 38673pif A compound which emits light (a luminescent compound) may be used, and a compound which is stable in shape of a film and exhibits strong luminescence ('and/or ray light') efficiency in a solid state is preferable. The light-emitting layer may be formed of a single layer or a plurality of layers, and may be formed of a light-emitting material (host material, dopant material). ^ The bulk material and the doping material may be one type or a combination of a plurality of types, either in any case. The doping material may be included in the entirety of the host material. • It may also be partially included, either in any case. As the doping method, it may be formed by a co-evaporation method with a host material, or may be simultaneously vapor-deposited after being mixed with a main material in advance. The amount of the host material used varies depending on the type of the host material, and can be determined according to the characteristics of the body material. The standard of the amount of the host material used is preferably from 5 〇 wt% to 99.999 wt% of the total luminescent material, more preferably 8 〇 '^% to 99.95 〖%, and the _ step is more preferably 90\¥ 1% ~ 99.9 correction / 〇. The amount of the doping material used varies depending on the type of the doping material, and can be determined according to the characteristics of the ruthenium doping material. The standard of the amount of the dopant used is preferably from 0 to 1 wt 〇 / 〇 to 50 Wt% of the total luminescent material, more preferably 〇〇 5 Wt / 0 to 20 wt%, and even more preferably 〇J wt%~i〇wt%. If it is in the above range, it is preferable in terms of, for example, prevention of concentration quenching. The luminescent material of the light-emitting element of the present embodiment may be either fluorifiable or luminescent. The main material is not particularly limited, and the town is suitably used: a condensed ring derivative which has been known as a illuminant and has been known as a luminescent ring, and a metal such as sigma 131 201224109 38673pif (- reduced porphyrin) Compounding 8_ ((10) face d) compound, bis-phenylethyl sulfonate: bismuthyl derivatives such as biological, tetraphenylbutadiene di-diamine derivatives, 嗓二哇 derivatives kiss each 幷^ = 4 raw:, cyclopentadienyl derivative, (tetra) derivative, 丄 = biological, pyrrole pyrrole derivative, g and polyphenylene (tetra) · Γ 1 in the polymer system. Bio-, poly-p-phenylene touches 'and poly-sales' as the main material, can be from the chemical industry 200; suitable for the listed parameters - compounds: and 'doping materials are not specifically limited to the illuminating color of nrtr from various materials select. ^ ^, for example, y: phenanthrene, anthracene, ketone, copper tetraphenyl, pentacene, flower, naphthalene = two, red fluorite, and benzophenone condensed ring derivatives, Saliva derivatives, benzopyrene derivatives, stupid: Yan: matter,. Plug: Evil:: a derivative, a biological, an azole derivative, a pyrroline derivative, a "biological, an ode derivative, a tetraphenyl derivative or a diphenyl benzene derivative S." _ Kaiping ^ 245087 Bulletin), double stupid diazonium (Japanese Patent Laid-Open No. 2_247278), :: "diazaindacene" derivatives, fur suits, Benkafu Bio, phenyl isophthalate, two (2, 4 , 6-triple base)

S 132 201224109 J8b/3pif isobenzopyrenes such as benzofuran, bis(2-mercaptophenyl)isobenzofuran, bis(2•trifluorodecyl)isobenzofuran, phenylisobenzofuran Furan derivative, dibenzofuran derivative, 7-dialkylamine coumarin derivative, 7-piperidine coumarin derivative, 7-hydroxycoumarin derivative, 7-oxime oxime Bean derivative, 7-acetoxycoumarin derivative, 3_benzothiazolyl coumarin derivative, 3_benzimidinocoumarin derivative, 3_benzoxanthene Coumarin derivatives such as coumarin derivatives, dicyanodecylpyran derivatives, dicyandi-yl-pyran derivatives, polymethine contacts, cyanine derivatives, pendant oxybenzoene Anthracene derivatives, dibenzo derivatives, rose red derivatives, luminosity derivatives, pyran derivatives, carb〇styril derivatives, acridine derivatives, oxazine derivatives, benzene Ether (phenylene 〇xide) derivative, quinacridone derivative, quinazoline derivative, pyrrole pyridine derivative, furopyridinium derivative, 1,2,5-thiadiazole derivative, pyrrole曱基(p Ymmiethene) derivative, benzalkonone derivative, pyrrole pyrrole $ biological, squarylium derivative, purpura_derivative, morphazine derivative, acridone derivative, deazaflavin derivative , anthracene derivatives, and stupid derivatives. If it is exemplified according to the color light, the blue to blue-green doping material may be exemplified by an aromatic hydrocarbon compound such as naphthalene, anthracene, phenanthrene, yum, yoke, sapphire, phenanthrene, or phenanthrene. , furan,. Biha, sigh, 矽heterocyclopentadiene, 9_矽苐, 9,9'-spirobifluorene, stupid thiophene, ^furan, anthracene, dibenzothiophene, dibenzofuran, imidazolium Aromatic ring compounds such as pyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolizidine pyridine, thioxanthenes or derivatives thereof, distyrylbenzene derivatives, tetrapyryl butyl 'di 133 201224109 38673pif olefin derived Substance, anthracene derivative, aldehyde-nitrogen derivative, coumarin, ..., sputum, sputum, sputum, sputum, sulphate, sulphate, sulphate, sulphate An aromatic amine derivative represented by N,_bis(3-nonylphenyl)-4,4'-diphenyl-1,1'-diamine. * and 'green to yellow doped materials can be cited as coumarin derivatives, phthalimide derivatives, naphthalene di(tetra)imine derivatives, purple ring gambling organisms, scale derivatives, rings Red (4) organisms, :: ketone derivatives, steroid derivatives, and fluorinated benzenes, etc., and the following compounds are also exemplified as suitable examples: In the exemplified compound, a aryl group may be introduced, and an amino group, an amine group, a nitrogen group or the like may be used for a long wavelength. Another 'orange to red doping material may be mentioned: a naphthylquinone or the like. Amine derivatives, acetophenone or acetoacetone or phenanthrene ketone and morphine are combined with bis-rare earth complex, 4 cyanomethylidene: alkenyl pyran or analog thereof An quinazoline derivative. More than derivatives, derivatives, etc., another:; ===, two butterflies as the above blue ~ basket ° as a suitable example: the introduction of the relevant compounds: color, and green ~ yellow doping materials and examples, Heteroaryl, aryl b, amine, 134, 201224109 38673pif, etc. The combination of long-wavelength substituents (4) is called silver (just represent silver) and also refers to the use of tris-metal complexes. A suitable example. -Pop is the phosphorescence of the central metal. In addition, as a dopant, it can also be selected from the 13th page of the wind, and the listed June issue of the Shenji Industrial Employment Co., Ltd.. The compound is equal to the above-mentioned doping material, the special product, the styrene-containing derivative organism containing the amine, and the phenanthrene derivative, the silver complex or the distillate compound. Listed: 3 1〇• cone 3,1.-bis(2,4,6-trimethylphenyl, '3, phenylphenyldiphenyl, hydrazine, 2,5,8,11-tetra-二丁美邡1 soil ^ , 4_ phenyl MU butyl 乂, 3,4,9,10• tetraphenyl flower, 3 must be, 11 · one (third butyl, 3 _ (9 , 's : (二苑, (第-butyl) and 'may also use Japanese Patent Special Kaiping (4) Bulletin, 曰本专利特开2000-133457号, 曰本面面-26324号, Japanese Patent Japanese Laid-Open Patent Publication No. 2001-267078, Japanese Patent Laid-Open No. 2001-267076, Japanese Patent Laid-Open No. Hei No. Hei. And an anthracene derivative described in JP-A-2001-217077, etc. Examples of the borane derivative include 1,8-diphenyl·1〇-(di(2,46-triphenyl) Boron-based, 9-phenyl-10-(bis(2,4,6-triphenyl) ruthenium), 4-(9'-S-yl)di(2,4,6-triazine) Phenyl) phenylnaphthalene, 4-(1〇,-phenyl-9,-onionyl) 135 201224109 38673pif bis(2,4,6-triphenylphenyl)borane, 9_(2 (2,4) ,6_triphenylphenyl)boron), 9-(4'-biphenyl)_10_(bis(2 4 6-triphenyl)phenyl), 9_(4,_(n_ 0 card 0) Phenyl)phenyl)-1〇-(bis(2,4,6-triphenyl)boro)phosphonium, etc. Further, borane described in the specification of International Publication No. 2000/40586 or the like can also be used. Examples of styrene-based derivatives containing amines include: ^, ^, _ tetrakis(4-biphenyl)_4,4,-diaminostilbene, n, N, N, N ,-tetrakis(1-naphthyl)-4,4'-diaminostilbene, n,n,N',N,-tetrakis(2-naphthyl)-4,4,-diaminodiphenyl Ethylene, N,N,-bis(2-naphthyl)-N,N,-diphenyl-4,4,-diaminodiphenylethylene, anthracene, fluorenyl--bis(9-phenanthryl)- N,N,-diphenyl-4,4,-diaminostilbene, 4,4L bis[4''-bis(diphenylamino)styryl]-biphenyl, 1,4- Bis[4,-bis(diphenylamino)styryl]-stupid, 2,7-bis[4,-bis(diphenylamino)styrene]-9,9-didecyl荞, 4,4'-bis(9-ethyl-3-carbazole extended ethylene)_biphenyl, 4,4'-bis(9-phenyl-3.carbazole extended vinyl)_biphenyl Wait. Further, an amine-containing styryl derivative described in JP-A-2003-347056, and JP-A-2001-307884, etc., may be used. Examples of the aromatic amine derivative include N, N, N, N-tetraphenylphosphonium-9, 1 〇-January, 9,1 〇-bis(4-diphenylamino-phenyl).蒽, 9,1〇_bis(4-di(p-naphthylamino)phenyl)anthracene, 9,10-bis(4-di(2-naphthylamino)phenyl)anthracene, 1〇_二_pair Tolylamino-9-(4-di-p-tolylaminonaphthyl)anthracene, 1〇-diphenylamino-9-(4-diphenylaminonaphthyl)anthracene, 1〇_二Phenylamino _9_(6-diphenylamino-2-naphthyl)anthracene, [4-(4-diphenylamino-phenyl)naphthalene "-yldiphenylamine, [4_(4 _Diphenylamino-phenyl)naphthalene-oxalyldiphenylamine,

S 136 201224109 38673pif [6-(4-diphenylamino-phenyl)-naphthylamine-1·yl]biphenyl, 44, _]-benylamine 4, bis-[4-diphenyl Bis(diphenylnaphthylamino)biphenyl, benzyl l-butylene, and the like. (4) Two copies of 本 · · 苯基 苯基 萘 萘 萘 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且 而且^报荨

The coumarin derivative may, for example, be coumarin-6 or coumarin. Further, the coumarin derivative described in the Japanese Patent Publication No. Hei. No. Hei. Examples of the pyridine pyran derivative include Dcm, DCJTB and the like described below. [化107]

Further, 'Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. 2005-097283, Japanese Patent Laid-Open No. Hei. No. 2002-234892, and Japanese Patent Laid-Open Publication No. 2001-220577. This patent is described in Japanese Laid-Open Patent Publication No. 2001-081090, and Japanese Patent Application No. 2001-052869. ratio. South derivative. Examples of the complex of the formula include Ir(ppy) 3 and the like described below. 137 201224109 , [Chem. 108]

Moreover, it is also possible to use Japanese Patent Laid-Open No. (H) No. 9398, Japanese Patent (4), No. 419, Pure, Japanese Patent Laid-Open No. 2,5, 298, 183, Japanese Patent Laid-Open No. 5-97726, and Japan The silver complex compound described in the Japanese Patent Publication No. 2_111137. The following complexes include PtOEP and the like. [109]

Et Et

s 138 201224109 38673pif ^And 'can also use Japanese Patent Special Open 2_· Japanese Patent Special Open Cong Yun No. Bulletin, Japanese Special ^ Men Brain - 093542 Bulletin, Japanese Patent Special Brain _335 = Two Japanese Patent Special Open 2 ^ as stated in the purchase bulletin and the like:

The electron-injecting layer of the electroluminescence element, the electron-transporting layer 〉=injection 〇7 functions to infiltrate the electricity from the cathode into the luminescent layer 1〇5 or the electron-transporting layer 106. The transport layer 1〇6 functions to inject electrons from the cathode ι8 into the human layer 1G7 into the luminescent layer 105. The electron transport layer 106 and the electron injection layer 107 are one or two of electron transporting and injecting materials. The above is layered, "formed, or formed by a mixture of an electron transfer wheel, a material for injection, and a polymer binder. The electron injection and transport layer is responsible for injecting electrons from the cathode and transporting electrons in a step-by-step manner. Ideally, the electrons are efficiently and efficiently transported into the injected electrons. Therefore, it is preferred that the electron affinity is large, the electron mobility is large, and the stability is excellent, and it is difficult to produce the impurity (10) at the time of production and use. However, when considering the balance between the transmission of holes and electrons, it is mainly possible to prevent the electricity from the anode from being combined and flowing to the celestial being, even if the electron transmission capacity is high. It still has the effect of improving luminous efficiency in the same way as the material of the electronic transmission. Therefore, the sub-injection and transport layer of the present embodiment can also include a function of efficiently preventing the layer from moving. θ The material (electron transport material) forming the electron transport layer 106 or the electron injection layer 107 can be a compound represented by the above formula (1).

The content of the compound represented by the above formula (1) in the electron transport layer 106 or the electron injection layer 107 varies depending on the kind of the compound, and can be determined depending on the characteristics of the compound. The standard of the content of the compound represented by the formula (1) is preferably from 1 wt% to 100 wt%, more preferably 10 wt% to 1%, based on the total amount of the material for the electron transport layer (or the material for the electron injection layer). 〇wt%, _ + is more preferably 50 wt% to 100 wt%, and particularly preferably 8 〇 wt%. In the case where the compound represented by the formula () is not used alone (100% by weight), other materials as described in detail below may be mixed. Other materials for forming an electron transport layer or an electron injecting layer may be used arbitrarily from the following compounds: a compound conventionally used as an electron transporting compound in a photoconductive material, an electron injecting layer and an electron electrically excited in an organic electroluminescence material. a well-known eight used in the transport layer

The material used in the electron transport layer or the electron injecting layer is more than at least one selected from the group consisting of a compound consisting of a material selected from the group consisting of carbon, sulfur, and zephyr. Scale derivatives and their condensed ring contacts, and metal complexes with 2 = accepting nitrogen. Specifically, it can be exemplified by ^=: 4,4,-bis(diphenylethylene) linkage; == biological side derivative, coumarin derivative, - formazan pure time, f thief benzene conversion _Bio, oxidation 140 201224109 38673pif _ biological H derivatives 'and ah derivatives. Examples of the metal-receptive compound having an electron-accepting rat include a trans-salt complex such as a phenyl-form complex, a methyl azide (azQmethine) complex, and a ruthenium complex.

(tr〇P〇1〇ne) metal complex, flavonol metal complex, and benzoquinolin metal misaligned scale. These materials can be used alone or in combination with different materials. "In terms of 'self-endurance, it is better to use 9,10-bis(2-naphthyl) anthracene, etc., 4 4, bis (diphenylethylene, styrene-based aromatic ring derivatives such as benzene, from bis(N-sitylene)), 1,3,5-di(]^-carbazolyl)benzene, etc. An azole derivative. Further, specific examples of the other electron-transporting compound include a naphthene other than the compound of the above formula (1), a naphthene other than the compound represented by the formula (1), a g derivative, a morphological organism, and a purple ring-salt creature. , fragrant bean organisms, naphthoquinones, bribes, gambling organisms, bi-p-benzoquinone derivatives, biphenyl derivatives, π-bidecene derivatives (1)-bis[(tetra)tributylphenyl (10)·.恶二峻ϋ, etc., sold pheno-touch, Sanzhao organism (Ν_naphthyl-2,5_diphenyl-m triazole, etc.), thiadiazole derivative, 8-hydroxyquinoline (oxine) derivative Metal complex, secret metal complex, ruthenium (tetra) derivative, abalone derivative polymer, &lt;*(4) compound, gallium complex, β 嗤 嗤 derivative, Α Phenyl derivative, triazine derivative, tazine derivative, and quinoline derivative (2,2'-bis(benzo[h]quinolin-2-yl)-9,9'-spiro Second-class) diimidazolium pyridine derivative 'borane derivative, benzimidazole derivative (tris(N-phenyl", oxime-2-yl)benzene, etc.), benzo. The cockroach derivative, benzopyrene, and the genus of the genus of the genus genus. ratio. Derivatives, hydrazine ill- 141 201224109.: pyridine derivatives, terpyridine derivatives (1,3-bis(4^(2,2,:67-tripyridyl))benzene, etc.), naphthyridine derivatives (bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldehyde nitrogen derivative, carbazole other than the compound represented by the above formula (丨) Derivatives, anthracene derivatives, phosphorus oxide derivatives, bisstyryl derivatives, and the like.

Further, a metal complex having electron-accepting nitrogen can also be used, and examples thereof include a 'hydroxyquinoline metal complex or a hydroxyphenyl oxazole compound hydrazine oxazole complex and a methine group. Nitrogen complex, tropolone metal complex, ketoxime metal complex, and kezhong gold deficiency. = The material can be made separately or mixed with different materials. The difficulty in the production of if4 is that (4) the green is a complex, a shout, a trans-base derivative or a benzoimene. Compound. The genus complex is represented by the following formula (5)) [Chem. 110]

(Ε-1)

Li, Al, Ga, Be Formula + ‘ R to R6 are hydrogen or a substituent, Μ is η, and η is an integer of 1 to 3. s 142 201224109 38673pif Specific examples of the hydroxyquinoline-based metal complex are 8 hydroxy 啥 钟 钟, 三 (8-经基喧琳), and 三(4-曱基-8-经基喧琳) Shao, San (5-fluorenyl-8-hydroxyquinoline), tris(3,4-dimethyl-8-hydroxyquinoline), tris(4,5-dimercapto-8-hydroxyquinoline Aluminum, tris(4,6-dimercapto-8-hydroxyquinoline) aluminum, bis(2-mercapto-8-hydroxyquinoline) (phenol)! Lu, bis(2-indolyl-8-hydroxyl) Quinoline) (2-methylphenol), bis(2-methyl-8-hydroxyquinoline) (3-mercaptophenone) aluminum, bis(2-mercapto-8-hydroxyquinoline) (4 -nonylphenol)aluminum, bis(2-indolyl-8.hydroxyquinoline)(2-phenylphenol)aluminum, bis(2-indolyl-8-hydroxyquinoline)(3-phenylphenol)aluminum , bis(2-indolyl-8-hydroxyquinoline) (4-phenylbenzene) aluminum, bis(2-mercaptohydroxyquinoline) (2,3-dimercaptophenol) aluminum, double (2- Mercapto-8-hydroxyquinoline) (2,6-diindolyl), bis(2-methyl-8-pyridyl) (3,4-dimercapto), aluminum, double (2-mercapto-8-hydroxyquinoline) (3,5-dimercaptophenol), bis(2-mercapto-8-hydroxyquinoline) (3,5-di-t-butylphenol) Aluminum, bis(2-mercapto-8-hydroxyquinoline) (2,6-diphenylbenzene) aluminum, double (2-mercapto-8-hydroxyquinoline) (2,4,6-triphenylphenol) aluminum, bis(2-mercapto-8-hydroxyquinoline) (2,4,6-tridecylphenol) Aluminum, bis(2-methyl-8-hydroxyquinolin) (2,4,5,6·tetradecylbenzene) aluminum, bis(2-mercapto-8-hydroxyquinoline) (1-naphthalene) Hope) aluminum, bis(2-mercapto-8-hydroxyquinoline) (2-naphthoquinone) aluminum, bis(2,4-dimethyl-8-hydroxyquinoline) (2-phenylphene) aluminum , bis(2,4·didecyl-8-hydroxyquinoline)(3-phenylphenol)aluminum, bis(2,4-dimercapto-8-hydroxyindole) (4-phenylbenzene) |Lu, bis(2,4-dimercapto-8-hydroxyindole) (3,5-dimercaptobenzene, 〇, bis(2,4-didecyl-8- 啥基啥琳) 3,5-di-t-butyl benzene age) aluminum, bis(2-mercapto-8-hydroxyquinoline) s-μ-side oxy-bis(2-mercapto hydroxyquinoline) aluminum, double (2,4-dimethyl-8-hydroxyquinoline)aluminum_μ_sideoxy_bis(2,4-didecyl-8-hydroxyquinoline)aluminum, bis(2-mercapto-4-ethyl Alkyl-8-hydroxyquinoline) Aluminium!!:: 143 201224109 38673pif -μ-Sideoxy·Bis(2-methyl- ice ethyl each via 啥 、, bis (2 methyl ice methoxy each)啥琳)Shaoqi-Sideoxy-bis(2-methyl-4-decyloxy-8-hydroxyindole) Ming, bis(2-methyl_5-cyano·8· 经基啥绍 侧 侧 侧 侧 侧 双 曱 曱 曱 曱 曱 曱 曱 曱 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双 双--Sideoxy-bis(2.methyl-5-trimethyl-decyl-quinoline) Aluminum, bis(10-phenylbenzo[h]quinoline), and the like. The bipyridine derivative is a compound represented by the following formula (E_2). [111]

(E-2) wherein G represents a simple bond or a n-valent linking group, and n is an integer of 2 to 8. True, carbon that is not used for the bonding of pyridine-pyridine or pyridine-G can also be substituted. G of the general formula (Heart 2) can be exemplified by the following structural formula. Further, R• in the structural formula is independently hydrogen, mercapto, ethyl, propyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or biphenyl. [化1口]

S 144 201224109 38673pif

Specific examples of the pyridine derivative include 2,5-bis(2,2'-bipyridyl-6-yl)-1,1-dimercapto-3,4-diphenylfluorene, 2,5-bis(2,2'-biacridin-6-yl)-1,1-dimercapto-3,4-di(2,4,6-triphenyl)anthracene 145 201224109 38673pif olefin, 2,5-bis(2,2'-linked 0-pyridin-5-yl)-l,l-dimercapto-3,4-diphenylfluorene heterocyclononadiene, 2, 5-bis(2,2'-bipyridin-5-yl)-1,1-dimercapto-3,4-di(2,4,6-triphenylene)fluorene heterocycle, 9 , 10-bis(2,2'-bipyridyl-6-yl)anthracene, 9,10-bis(2,2,-bipyridin-5-yl)anthracene, 9,10-di(2,3'- Bipyridyl-6-yl) fluorene, 9,10-bis(2,3'-bipyridin-5-yl)indole, 9,10-di(2,3'-bipyridyl-6-yl)-2- stupid Base, 9,10-bis(2,3,-bipyridin-5-yl)_2_phenylindole, 9,10-di(2,2'-bipyridin-6-yl)-2-phenyl蒽, 9,10-di(2,2 匕bipyridyl-5-yl)-2-phenylindole, 9,10-bis(2,4'-bipyridin-6-yl)-2-phenylindole, 9,10-bis(2,4'-bipyridin-5-yl)-2.phenylanthracene, 9,10-bis(3,4,-bipyridyl-6-yl)-2-phenylindole, 9 , 10-bis(3,4'-biacridin-5-yl)-2-phenylindole, 3,4-diyl-2 , 5-bis (2,2'-linked π ratio α--6-yl) ° phenanthrene, 3,4·diphenyl·2,5-di(2,3,-bipyridyl)thiophene, 6 , 6', -di(2-pyridyl) 2,2,:4,,4,,:2,,, 2μ, _tetraacridine, and the like. The phenanthroline derivative is a compound represented by the following formula (Ε-3-1) or the formula (Ε_3_2). [化113]

In the formula, R to R8 are a hydrogen or a substituent. The adjacent groups may be bonded to each other to form a condensed ring, and G represents a bond of a material or a valence of η. Further, the oxime of the formula m 2 2 formula 1 3-2) can be exemplified by the specific example of the phenanthroline derivative of the bipyridyl 146 201224109 38673pif bite derivative (IV). - 2, 9_ Dimethyl-4,7-diphenyl-u〇 sold, 9, i〇:=U〇-morph, i, 2,6-di (1,10-morphine_5_yl) u :( , 0_morphine-2-yl) benzene, keto difluoride double (1,10 • brown heart, 3f three (1 calculation of brown-based) - U0- morphine (bath〇cuproine) or plant; Base · 4,7-biphenyl) benzene and the like. One, bis(2-styl·1,10-morphine-9- Φ is especially useful for the case where a phenanthroline derivative is used. In order to pass a long time layer, an electron injecting layer or an adjacent substituent The steric repulsion is due to the fact that the compound of the structure of the morphine is linked to the structure of the morphine, or the structure of the lining of the lining, the "aroma of the substitution", the substitution or the The compound of the squeezing type (Ε·4) is disclosed in detail in Japanese Patent Publication No. 27587.

Υ—X

(Ε·4) 147 201224109 38673pif If the United States M is divided into hydrogen, silk, and can also be replaced by ^ less one _, silk, can also be substituted nitrogen-containing heterocyclic ring, or cyano-R 6 independent It can also be substituted by a == group, which can also be substituted with an aryl group = an aryl group of 16 or less, a substituted boron group or a substituted carbazole, and η is independently 0~ An integer of 3. In the compound represented by the formula (Ε_4), a compound represented by the following formula (Ε-4·1) is preferred, and a compound of the following formula (4) is more preferred. 1-4) The compound represented. Specific examples include ά(4_bis(2,4,6.triphenyl)borylnaphthalen-1-yl)phenyl]carbazole, 9-[4-(4-di(2,4,6_) Trimethylphenyl)borylnaphthalen-1-yl)naphthalen-1-yl]carbazole and the like. [化115]

N-X1

(E-4-1)

Wherein R11 and R12 are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, a substituted nitrogen-containing heterocyclic ring, or at least one of cyano groups, and Rn~Ri6 are each independently The alkyl group which may also be substituted or the aryl group which may be substituted, R21 and r22 are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, or a substituted aza-containing ring,

S 148 »11 201224109 is an integer of ～3 which can also be substituted with a carbon number of 20 or less, and is divided into at least one of cyano or cyano, χ1 is an aryl group, and η is independently an integer of 〇4. [化116]

R35

In each formula, 'R31 to R34 are each independently a methyl group, an isopropyl group or a phenyl group, and each of R35 and R36 is independently hydrogen, methyl, isopropyl or phenyl. Among the compounds represented by the above formula (E-4), a compound represented by the following formula (E-4-2) is preferred, and a compound represented by the following formula is more preferred. [化117] 149 201224109 38673pif

Wherein R11 and R12 are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, a substituted gas-containing hetero ring, or at least one of an aryl group, and R13 to R16 are each independently The aryl group X X which may also be substituted or substituted may be an extended aryl group having a carbon number of 2 Å or less, and η is independently an integer of 〇 3 . [化118]

In the formula, R31 to r34 are each independently an indenyl group, an isopropyl group or a phenyl group, and R35 and R36 are each independently hydrogen, methyl, isopropyl or phenyl. Among the compounds represented by the above formula (E-4), preferred are compounds represented by the following formula (E-4-3), more preferably the following formula (E-4-3-1) )

S 150 201224109 or a compound represented by the formula (E-4-3-2). [化119]

Wherein R11 and R12 are each independently hydrogen, an alkyl group, a substituted aryl group, a substituted decyl group, a substituted nitrogen-containing heterocyclic ring, or at least one of cyano groups, and R13 to R16 are each independently Is an alkyl group which may also be substituted, or an aryl group which may also be substituted, XI is an optionally substituted aryl group having a carbon number of 10 or less, and Y1 is an aryl group which may also be substituted with a carbon number of 14 or less. And η is independently an integer of 0 to 3, respectively. [化120]

In each formula, R31 to R34 are each independently a methyl group, an isopropyl group or a phenyl group 151 201224109 38673pif, and each of R35 and R36 is independently a hydrogen, a decyl group, an isopropyl group or a phenyl group. The benzimidazole derivative is a compound represented by the following formula (E-5). [化121]

In the formula, Arl to Ar3 are each independently hydrogen or an aryl group having a carbon number of 6 to 30 which may be substituted. Particularly preferred is Arl which is a benzoimidazole derivative which may also be substituted. Specific examples of the aryl group having a carbon number of 6 to 30 are: phenyl, 1-naphthyl, 2-n-based, dangerous-1-yl, dangerous-3-yl, dangerous-4-yl, dangerous-5-yl. , indol-1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-9-yl, fluoren-1-yl, |chrom-2-yl, 1-phenanthryl, 2 - non-based, 3-nonyl, 4-nonyl, 9-phenanthryl, 1-isolated, 2-onionyl, 9-fluorenyl, olean-1-yl, fluoran-2-yl, fluoranthene -3-yl, fluorescein-7-yl, camp-on-8-yl, extended diphenyl-1-yl, extended diphenyl-2-yl, H-1-yl, ke-2-yl, 芘-4 -yl, 1,2-benzophenan-1-yl, 1,2-benzophenan-2-yl, 1,2-benzene is not-3-yl, 1,2-benzophen-4-yl, 1,2-benzophenan-5-yl, 1,2-benzene, non-6-yl, thick tetra-l-yl, thick tetra-2-yl, slightly tetra-5-yl, :j£-l-yl, ;-2-yl,; ι£-3-yl, fused pentaphenyl-1-yl, fused penta-2-yl, fused five--5-yl, thick five- 6-based. 201224109 38673pif this = m _ biological specific examples are: i phenyl 2_ (4 _ (ig • phenyl poor winter base) stupid) - m - stupid [d] sodium saliva, 2_ (4 ^ based H-benzene Base-m-stupid [d]_, 2 naphthalene^ base (naphthalene I group = one base-1H-open [d]imidazole, H4_(yl)-2-phenyl-1H-stup [ d] taste saliva, 2 (9 ^ 2) ^)

Base)-1,2-diphenyl-1H-benzo[d]imidazole.丞) The electron transport layer or the *fBi layer is formed in the electron transport layer or the electron injection layer; the @ step includes the substance which can be used if the substance has a certain reducing property. The reducing property is suitably selected from the group consisting of a substance such as an organic complex of a soil which can be used for soil testing, and a rare earth metal, and a preferred reducing substance: Na (^ = number is 2) , (the work function is, ^ substance: the good work function is 2.9ev or less. These - step ^ 2 ^ ^ ^ test metal 'into better 疋 Rb or Cs, the best is Cs. The metal, especially 153 201224109, has a high reduction ability and is injected by a small number of sub-injection layers, which can be used to form an electron transfer layer or to have a high or long life, and the luminance of the Tmf/L element. Substance; these are: - gold == the following combination of reducing Cs, such as cs 盥 Na, c = preferably 'excellent' is a combination of Na and K. By m_b, or Cs The force, and the addition of the material/effectiveness to the reduction energy, can realize the material of the light-emitting layer of the organic EL element (the cathode of the organic electroluminescence element) or the long life. Electron: Injecting electrons into the light-emitting layer (10) and the electron transport layer is organic: if the material can efficiently inject electrons into π the same substance. Among them, preferred are: tin bismuth silver, copper, nickel, chromium, gold, molybdenum, 钟Μ Λ. ^ , 'iron, zinc, lithium, sodium, potassium, strontium, and genus or some Alloys of metals (magnesium-silver alloys, magnesium-indium alloys, fluorine's, etc.), etc. In order to improve the efficiency of electron injection, the characteristics of the parts are improved. The effective ones are clock, sodium, unloading, recording, and mother. , magnesium, or alloys of low-work function metals. However, these low work function metal suspensions are unstable in the atmosphere in most cases. To improve this, for example, it is known to dope in organic layers. A method of using a stable electrode with a small amount of a clock, strontium or magnesium. As other dopants, inorganic salts such as gasification, cesium fluoride, lithium oxide, and cerium oxide may also be used. Limited to these substances.

S 154 201224109 38673pif In addition, the following methods are exemplified as preferred examples: alloys of some metals such as layers, gold, silver, copper, iron, tin, sulphur, and indium, and sulphur dioxide, titanium dioxide, and ΓΓΐί machine, polyvinyl alcohol, polyvinyl chloride, _ polymer compound = electric t electrode can also be made by heating, electron beam, money, ion =, and (four), etc. System limits. <Binders that can also be used in each layer> The above-mentioned hole injection layer, hole transport layer, light-emitting layer, and electron-injection layer-like material can form each layer separately, and the knife is placed in the following molecular bonding. Financial system: ;; purpose = Ethylene, poly (tetra)-based horror polythiol C 2 = methacrylic acid butyl vinegar, poly vinegar, poly milling, polystyrene scale, polybutylene dilute, furnace resin, _ lipid, phenoxy Solvents such as base resin, poly-, ethyl cellulose, acetamethylene glycol vinegar resin, ABS resin, polyamine phthalic acid vinegar resin, etc., or transesterification, xylene resin, petroleum resin, urea resin, trimeric urethane resin A curable resin such as an unsaturated poly-lipid, an alkyd resin, or an epoxy resin gas resin. &lt;Production Method of Organic Electroluminescence Element&gt; Each layer constituting the organic electroluminescence element can be subjected to vapor deposition, resistance heating vapor deposition, electron beam level, Lai, molecular method, printing method, and casting The method or the coating method is formed by forming a film of each layer into a film. The film thickness of each layer formed in this manner is not particularly limited and may be appropriately set depending on the nature of the material, and is usually in the range of 2 nm to 5 mm. It is often made by ^英振i-type film thickness; receiving device, etc. 155 201224109 J80/ipif When the film is thinned by yttrium plating, the evaporation conditions are due to the type of material and the target crystal structure of yttrium. And the association structure and so on. The preferred vapor deposition conditions are usually at the boat heating temperature + 5 (rc~+ gamma. C, vacuum degree 1〇-6Pa~1G_3 Pa, evaporation rate G.G1 nm/see~5Gnm/sec, plate) , -15 (TC ~ + 30 (rc, film thickness 2nm ~ 5 Qing is suitable to set. Next] as an example of the method of making organic electroluminescent elements,

A method for fabricating an organic electroluminescent device having the following structure: an anode/hole injection layer/hole transport layer/light-emitting layer/f sub-transport layer/electronic injection layer composed of a host material and a dopant material /cathode. On a suitable substrate: an anode is formed by forming a thin film of the anode (four) by vapor deposition method, and a film of a hole injection layer and a hole transport layer is formed on the anode. Forming a light-emitting layer on the composite material and the doping material, forming an electron-transporting layer, an electron-injecting layer on the light-emitting layer, and forming a thin film by a base mineral method And forming a cathode, thereby obtaining an organic electroluminescence element. In addition, the above organic electroluminescence element

In the X process, the fabrication sequence may be reversed, and the cathode, the electron injection layer, the electric t-transport layer, the light-emitting layer, the hole transport layer, the hole injection layer, and the anode may be fabricated in this order. The XY of the DC voltage is applied to the organic electroluminescence device thus obtained, the polarity of the % electrode is set to +, and the polarity of the cathode is set to be read: If the applied voltage is 2 V to 4 〇 Around V, light can be observed from the electrode side of the transparent or ▲ (anode or cathode, and both poles). However, the organic electroluminescence element can also emit light when a pulse current C0 156 201224109 38673pif or an alternating current is applied. In addition, the waveform of the applied alternating current may be an arbitrary waveform. &lt;Application Example of Organic Electroluminescence Element&gt; Further, the present invention can also be applied to a display device having an organic electroluminescence element or an illumination device having an organic electroluminescence element or the like.

A display device or an illumination device having an organic electroluminescence device can be manufactured by a known method such as connecting an organic electroluminescence device of the present embodiment to a known driving device, and can be suitably driven by a DC drive or a pulse drive. The AC drive is known to be driven by the purchase method. (4) The device includes, for example, a panel display such as a color flat panel display, and a flexible display such as a (9) organic electroluminescence (EL) display. See Japanese Patent Laid-Open No. Hei 3, Japanese Patent Publication, and the like. ^And, "ϋ 〗 〖Septe. Further, the moments g and t may be, for example, a matrix and/or a panel. The transition and the segment display may also coexist in the same S. The stomach matrix is used to display a check or a mosaic, etc., and the shape or size of the austenoid is arranged in a lattice shape by the use of j. / Display text or images. The image and text of the venetian TV are computer, monitor, and quadrilateral, and when the display is less than 300 divisions, the use of a large display with a side of millimeters is the same as the color of the same color. It can be arranged; in the case of ~ monochrome, the green and blue scorpion will be rewarded with a wide color display, which will be red. In this case, there is a typical triangular shape (delta 201224109 38673pif n and Stripe type (one etype). * and 'The driving method of the matrix can be the line order une seq reward (4) driving method or active matrix (active matrix of any kind. Line order driving has the advantage of simple structure, but in the action In the case of characteristics, there is a case where the active matrix is excellent, so it must be used flexibly according to the purpose.

In the segment type (type) towel, a predetermined pattern is used to form a pattern to cause the determined region to emit light. For example, a digital clock (10) lion clock) or a temperature-dependent or temperature-aged, sound-receiving or induction cooker operation state display, and a panel display of a car. For example, a lighting device such as an indoor lighting or a backlight of a liquid crystal display device can be used. For example, refer to Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. 2003-277741, Japanese Patent Laid-Open No. 2003-277741 Bulletin, etc.). The backlight is mainly used for improving the visibility of a display device which does not emit light by itself, and is used in a liquid crystal display device, a clock, an audio device, an automobile panel, a display panel, and a logo. In particular, in consideration of the following aspects, the backlight using the light-emitting element of the present embodiment is characterized by being thin and lightweight: as a liquid crystal display device, in particular, a backlight for personal computer applications in which thinness is a problem The device of the prior art is constituted by a fluorescent lamp or a light guide plate and is difficult to be thinned. [Example]

<Synthesis Example of Compound represented by Formula (1-335)> Stage 1: 2-naphthylboronic acid (1.9 g), bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzene [c]carbazole _5,9-diester (5.9g), potassium acetate (〇.〇2g), triphenylphosphine (Tpp) (〇.03g), potassium phosphate (K3P04)

The flask of S 158 201224 wins (8.5 g) and tetrahydrofuran (THF) / isopropanol (IPA) solution (3:1 by volume) (30 ml) was stirred under a nitrogen atmosphere at reflux temperature for 0.5 hour. The reaction solution was cooled to room temperature, and water and ethyl acetate were added to conduct liquid separation, and the solvent was evaporated under reduced pressure. The obtained solid was washed with methanol to give 9-(naphthalen-2-yl)-7-phenyl-7H-benzo[c]oxazol-5-yl trifluorosulfonate (5.4 g). Stage 2: 9-(naphthalene-2-yl)-7-phenyl-7H-benzo[c]oxazol-5-yl trifluoromethanesulfonate (5.4 g), boranoic acid pinacol Ester (3.〇g), (1,1'-bis(diphenylphosphino)ferrocene) digas palladium (II) (Pd(dppf)cl2) (0.16g), potassium acetate (2.9g) A flask of cyclodecyl mercapto ether (CPME) (3 〇 ml) was stirred at reflux temperature for 4 hours. The reaction liquid was cooled to room temperature, and water and ethyl acetate were added to conduct liquid separation, and the solvent was evaporated under reduced pressure. The obtained solid was washed with decyl alcohol to obtain 9-(naphthalen-2-yl)-7-phenyl-5-(4,4,5,5-tetradecyl-1,3,2-dioxa Cyclopentyl bromide_2_yl)-711_benzo[[sigma] card. Sit (4.9 g). 9-(naphthalen-2-yl)-7-phenyl-5-(4,4,5,5-tetradecyl-1,3,2-oxo-heterocyclic ring obtained as described above will be charged. Pentan burns 2_base)·7η_benzo[c]carbazole (4.9 g), 2-(4-diphenyl)nbipyridine (25 g), pd(pph3)4 (〇3 g Potassium phosphate (K3P04) (12.0 g) and a flask of + tridecylbenzene (pseudocumene) (50 ml) were stirred at reflux temperature. After cooling the reaction mixture to room temperature, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water, washed with methanol, further washed with heptane, and purified by activated alumina column chromatography (developing solution: benzene/ethyl acetate mixed solvent). . At this time, refer to "Yes!; 159 201224109 38673pif Machine Chemistry Experiment (1) - Substance Usage and Separation and Purification - "Chemical Tongren Co., Ltd., published on page 94, to make the acetic acid in the developing solution The ratio of the ester is gradually increased to dissolve the target. After distilling off the solvent under reduced pressure, the obtained solid is dissolved in chlorobenzene by heating, and heptane is added to carry out reprecipitation to obtain a compound represented by the formula (1-335), that is, 9-(naphthalen-2-yl)- 7-Phenyl-5-(4-(.pyridin-2-yl)phenyl)-7H-benzo[c]carbazole (3.3 g). [化122]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 8.93 (d, 1H), 8.71 (d, 1H), 8.68 (m, 1H), 8.06 (d, 2H), 8.01 (d, 1H), 7.95 (s , 1H), 7.83 -7.93(m, 3H), 7.70 - 7.80(m, 7H), 7.58 - 7.65(m, 5H), 7.55(s, 160 s 201224109 38673pif !Η), 7.46 - 7.52(m, 3H 7.41 (t, 1H), 7.2 (m, 1H). &lt;Synthesis Example of Compound represented by Formula (1-140)> 9-(naphthalen-2-yl)-7-phenyl group -5-(4,4,5,5-tetradecyl-1,3,2-dioxaborolan-2-yl)-7H-benzo[c]carbazole (1.0 g), 5 -Bromo-2,3'-linked 0-bite (0.5 g), bis(dibenzylideneacetone)-sodium (Pd(dba)2) (0.05 g), tricyclohexylphosphine (Cy3P) (〇 The flask of 〇5g), potassium phosphate (K3P04) (1.2 g) and I,2,4-trimethyl stupid (pseudo cumene) (6ιη1) was stirred at reflux temperature for 16 hours. After the reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by suction. The obtained solid is washed with water, and the second cleaning is carried out by heating and washing with helium. After the column chromatography (expansion liquid: toluene/acetic acid ethyl acetate mixed solvent), 沌, chaotic . At this time, after the acetic acid in the developing solution is removed from the solvent, the obtained == and the present is added with heptane to reprecipitate to obtain the formula (1_14〇) which is stupid, that is, 5_((2,3'· Joint _5·基)_9_(naphthalene_2_yl)^ Benki·7Η_stupid [e] material (〇7g). [Chem. 123]

(M40)

C 161 201224109 if The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): δ = 9.26 (d, 1H) 9 1H), 8.97 (d, 1H), 8.80 (d, 1H), 8.67 (d, 1H), 8.39' (m out ' 8.10 (dd, 1H), 8.05 (d, 1H), 7.99 (m, m), 7.96 _ 7^'4 ' 2H), 7.90 (m, 1H), 7.85 (d, 1H), 7.80 (t, 1H) , 7 74 / called (m, 2H), 7.68 - 7.62 (m, 5H), 7.59 (s, 1H), 7.55 - 7.50 (m, 3 44 (m, 2H). ,,. &lt; Synthetic Example of the Compound Illustrated by 212) 9-(Naphthalene-2-yl)-7-phenyl.5-(4,4,5,5-tetramethyl I)? Dioxedane Pentaborane-2-yl)-7Η-benzo[c]carbazole (3.〇g), 2'3/bipyridine (1.6 g), bis(dibenzylideneacetone)palladium (〇) 5 2's hexyl phosphine (0.5 g), constitutively potassium (K3P04) (8.8 g) and j 24 benzyl (pseudo-lean) (18 ml) flask will be thrown at 4 rpm at reflux temperature After the reaction solution was cooled to room temperature, water was added, and the precipitated solid was collected by suctioning. The obtained solid was washed with water, followed by methanol washing, main washing, and further heating and washing by g-burning. Separation by active oxidation column column (deion solution: toluene / B The ethyl ester mixed solvent is purified. At this time, θ is gradually increased in the ratio of ethyl acetate in the developing solution to elute the target. After the solvent is distilled off under reduced pressure, the obtained solid is heated and dissolved in the gas benzene, and added. Re-precipitation by calcination to obtain a compound represented by the formula (1-212), that is, 5_((2,3'-linked) is more than π)-6 base)_9·(naphthalene_2_yl)_7_ stupid Base _?Η•Benzene[c]. Card 0 sits (0.8 g). [Chem. 124] 162 201224109 38673pif

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 9.34 (d, 1H), 9. 〇〇 (d 1H), 8.79 (d, 1H), 8.68 (m, 1H), 8.46 (m, 1H), 8.28 - 8.26 (m 2H), 8.04 (d, 1H), 7.99 (m, 1H), 7.94 - 7.84 (m, 6H)5 7.8〇(t 1H), 7.72 - 7.66 (m, 4H), 7.66 (m, 2H), 7.54 (m, 3H), η 44 (m, 2H). l, 1-4J1 a w I々~ mouth / will be loaded with trifluoromethanesulfonic acid 9-(naphthalene-2-yl)_7• stupid基_7扎笨十坐-5-基酉(3·0 g), 3-(3-(4,4,5,5_tetramethyl), 3,2_ j 戍-2-yl) Phenyl) bite (1.8 g), acetic acid (〇〇1 g), tris 2, 〇'〇3 g &gt; phosphorus _U3K) 4 4·5 g ), and THf/isopropanol 1 ' : read The product ratio is 3 : 1) (20ml) &lt;The flask is back 6 =. Add anti-gross light to room temperature and add water, by =, clever solid. The obtained solid was called washed, heated and washed with heptane, and purified. At this time, the ratio of acetic acid (f) in the developing solution was gradually lowered. 163 201224109 38673pif The target was eluted. After removing the solvent from the decompressed crane, the obtained solid is heated and dissolved in gaseous benzene, and heptane is added to carry out reprecipitation to obtain a compound represented by the formula (1-431), that is, 9-(naphthyl K7-phenyl- 5-(3-7-pyridin-3-yl)·7Η-stupid [c]carbazole (1.7 g) ° [Chem. 125]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 8.97 (d5 1H), 8.92 (d 1H), 8.76 (d, 1H), 8.63 (d, 1H), 8.05 (d, 1H), 7.99 (m, 1H) ) 7.96 · 7.85 (m, 5H), 7.83 - 7.70 (m, 4H), 7.70 - 7.60 (m, 5H)' · 7-6〇- 7.48 (m, 6H), 7.45 (t, 1H), 7.39 (m, 1H). 'Synthesis of a compound represented by the formula (1-383)&gt; 9-(naphthalen-2-yl)-7-phenyl-5-(4,4, 5,5-tetradecyl-1,32 dioxaborolan-2-yl)-7H-benzo[c]carbazole (2.0 g), 4-(4^odoryl)pyridine (1.0 g ), bis(dibenzylideneacetone)palladium(0) (0.32, monocyclohexylphosphine (0.31 g), potassium phosphate (K3P04) (5.8 g) and: methylbenzene (pseudocumene) (I2 ml) When the flask was centrifuged at reflux temperature, the reaction solution was cooled to room temperature, and water was added to extract the main solid. The obtained solid was washed with water, and then washed with water. After heating and washing with the domain money, it is purified by active oxidation B column chromatography (expansion liquid: f stupid/acetic acid ethyl acetate mixed solvent). At this time, the ratio of B to the liquid towel is slowed down. Increase and dissolve After the solvent is removed from the dragon, the obtained solid is heated and dissolved in chlorobenzene 7Γ.

Re-precipitation by adding heptane to obtain a compound represented by the formula (1_383), that is, 9-(naphthalene-2-yl)-7-phenyl-7-(4-tetradecyl)phenyl][C] Carbazole (l.Og). [化126]

(1-383) The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5=8.97 (d, 1H), 8.76 (d, 1HX 8.69 (d, 2H), 8.05 (d, 1H), 7.99 (m, 1H), 7.95 - 7.92 (m , 2H), 7.89 (m, 1H), 7.83 (d, 2H), 7.81 - 7.73 (m, 5H), 7.72 -7 63 (m, 5H), 7.58 - 7.51 (m, 6H), 7.46 (t, 1H). &lt;Synthesis Example of Compound represented by Formula (1-384)&gt; The first stage will be loaded with 1-carotonic acid (4.5 g), double (three defeats continuation 165 201224109 38673pif acid) 7 -Phenyl-7H-benzo[φ卡嗤-5,9二基酷(14〇g), acetic acid (0.08 g), diphenylphosphine (0.18 g), potassium phosphate (K3p〇4) (2 〇14g) and THF/isopropyl alcohol (IPA) solution (volume ratio 3: υ (8〇ml), bottle under nitrogen atmosphere, reflux temperature for 5 hours. Add cold reaction to room temperature' After the water and the acetic acid are separated, the solvent is removed. The obtained m body is washed with methanol to obtain trifluoromethane 9_(Cai+yl)-7-phenyl-7H-benzo[c]. Oxazol-5-yl ester (n 〇g). Stage 2: will be loaded with trifluoromethyl acid 9_(Cai Xiaoji)_7_phenyl 7H-benzo[c]oxazol-5-yl ester (nog) , boranoic acid pinacol ester (5 9 §), (1,1-bis(diphenylphosphino) The flask of diferrocene (11) (〇57 吕), acetamidine, (5.7 g) &amp; cyclopentyl fluorenyl hydrazine (6Qml) was mixed at reflux temperature for 3 hours. The reaction solution was cooled to room. After adding water and ethyl acetate to separate the liquid, the solvent was removed under reduced pressure. The solid obtained was washed with methanol to obtain 9-(naphthalen-1-yl)·7-phenyl_5_(4,4 5 , 5_tetradecyl _13 2 -dioxaborolan-2-yl)-7H- benzo[c]carbazole (69 g). 9_(naphthalene small) obtained as described above Phenylphenyl (4,4,5,5-tetradecyl-1,3,2-dioxaborolan-2-yl) 7H benzo[c]carbazole (1.0 g), 2-( 4- Desert phenyl) acridine (〇5 g), bis(dibenzylidenepropyl), palladium (0) (〇.16g), tricyclohexylphosphine (〇15 g), potassium phosphate (K3p〇4) The flask of at9 g) and 1,2,4_tridecyl (pseudo-decene) (6 ml) was mixed for 5 hours. The reaction solution was cooled to room temperature, water was added, and the precipitate was collected by suction filtration. Solid. The obtained solid was washed with water, washed with methanol, and heated by heptane. 4 by activated alumina column chromatography (developing solution: toluene/acetic acid B) Ester 201224109 joo/jpif mixed solvent) for purification. At this time, the ratio of the acetic acid in the developing solution is gradually increased to elute the target. After distilling off the solvent under reduced pressure, the obtained solid is dissolved in chlorobenzene by heating, and heptane is added to carry out reprecipitation to obtain a compound represented by the formula (1-384), that is, 9-(naphthalen-1-yl)- 7-Phenyl-5-(4-(acridin-4-yl)phenyl)-7H-benzo[c]carbazole (0.7 g). [化127]

(1-384) The structure of the compound obtained by cancer was determined by NMR measurement. 1H-NMR (500MHz, CDC13): δ = 8.97 (d, 1H), 8.78 (d, 1H), 8.69 (d, 2H), 7.95 (t, 2H), 7.84 (d, 2H), 7.80 - 7.73 ( m, 5H), 7.67 - 7.50 (m, 10H), 7.47 - 7.41 (m, 3H), 7.32 - 7.27 (m, 2H). 167 201224109 38673pif <Synthesis of a compound represented by formula (1-376)> Stage 1: Incorporation of phenyl arsenic acid (3 2 g), bis(trifluoromethane) 7-phenyl-711-benzo[[;;]carbazole-5,9-diyl Ester (14.〇8), palladium acetate (0-04g), trisylphosphine (0.09 g), phosphate (K3P04) (20.17 g) and THF/isopropanol (IPA) solution (volume ratio 3: 1) (80 ml) The flask was stirred under a nitrogen atmosphere at reflux temperature for 3.5 hours. The reaction solution was cooled to room temperature, and water and ethyl acetate were added to separate the mixture, and the solvent was evaporated under reduced pressure. The solid was washed to obtain 7,9-diphenyl-7H-benzo[c]oxazolyl trifluoromethanesulfonate (9.6 g). Stage 2: loaded with trifluoromethanesulfonic acid 7,9_ Diphenyl-7H• benzo[c]carbazol-5-yl ester (9.6 g), boronic acid pinacol ester (5.6 g), (1,1,·bis(monophosphazyl) ferrocene Iron) two gas handles (H) (〇53 g) The flask of potassium acetate (5.5 g) and cyclopentyl decyl ether (55 ml) was stirred at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and water and ethyl acetate were added for liquid separation, followed by distillation under reduced pressure. Solvent. The obtained solid was washed with decyl alcohol to obtain 7,9-diphenyl-5-(4,4,5,5-tetradecyldioxaborolan-2-yl)-7H-benzene. And [c]carbazole (7.9 g). The 7 9-diphenyl-5-(4,4,5,5-tetramethyl-1,3,2-di which was obtained as described above was charged. Oxacycloborane-2-yl)_711_benzo(4)carbazole (i 〇g), 2-(4-&gt; stinky base) π ratio σ (〇6g), bis(di-subunit) Acetone)! Bar (〇) (0.17 g), tricyclohexylphosphine (〇.17 g), potassium phosphate (K3P〇4) (2 9 g) and 1,2,4-trimethylbenzene (fake (6 mi) The flask was stirred at reflux temperature for 14 hours. After cooling the reaction mixture to room temperature, water was added. The precipitated solid was collected by suction filtration. The obtained solid was washed with water, followed by 201224109, u. , decyl alcohol is washed, further heated and washed by g-burning, and then subjected to activated alumina column chromatography (deion liquid: benzene/ethyl acetate mixed) The solvent) to be purified. At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. After distilling off the solvent under reduced pressure, the obtained solid is dissolved in benzene by heating, and then re-precipitated by adding heptane to obtain a compound represented by the formula (1-376), that is, 7,9-diphenyl-5- (4-(Pyridin-4-yl)phenyl)-7H-benzo[c]carbazole (0.5 g).

[化128]

The structure of the obtained compound was grafted by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 8.95 (d, 1H), 8.74 (d, 1H), 8.68 (d, 2H), 8.02 (d, 1H), 7.85 - 7.70 (m, 7H), 7.65 - 169 201224109 38673pif 7.62 (m, 4H), 7.58 - 7_43 (m, 10H). &lt;Synthesis Example of Compound represented by Formula (1-360)&gt; 9-(naphthalene-1-yl) -7-phenyl-5-(4,4,5,5-tetramethyl 3 2 dioxaborolan-2-yl)-7H-benzo[c]carbazole (L4 g), 3 :(4^臭笨基)°°°(〇.6 g), bis(dibenzylideneacetone)|bar (〇) (〇〇5 g),,: cyclohexylphosphine (ο·〇3 phosphoric acid) A flask of potassium (k3p〇4) (I] g}, ethanol (1 ml) and water (1 ml) was stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature and methanol was added by suction. The precipitated solid was washed with water, and then washed with decyl alcohol, and then subjected to column chromatography using an amine-based modified silicone (NHDM1020: manufactured by Fuji Silysia) (developing solution: toluene). Purification is carried out. After distilling off the solvent under reduced pressure, the obtained solid is recrystallized from ethyl acetate to give the compound of formula (1-360), that is, 9·(naphthalen-1-yl)-7-benzene. -5-(4-(π|^π定-3-yl)phenyl)-7H-benzo[c]indole (1.1 g).

S

1H-NMR (500 MHz, CDC13): 5=8.98 (d, 1H), 8.92 (d, 170 201224109 38673pif 1Ηλ 8.78 (d,1H), 8.61 (dd,1H),7.93 (m,3H),7.82 ( d, 2H), 7·75 K 3H), 7.68 (d, 2H)} 7.63 (d, 2H), 7.60 - 7.52 (m, 6H), 7·48 - 7.42 (m, 3H), 7.38 (dd, 1H), 7.32 - 7.26 (m, 2H). &lt;Synthesis Example of Compound represented by Formula (1-408)&gt; 9-(Naphthalene-1-yl)-7-phenyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-711-benzo[c]carbazole (1.4 g), 2-(3 -Bromophenyl)pyridine (0-6 g), bis(dibenzylideneacetone)palladium (0) (0.05 g), tri-cyclohexylphosphine (0.03 layer), potassium phosphate (0?04) (1.1§), A flask of toluene (91111), ethanol (EtOH) (1 ml) and water (1 ml) was stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature and decyl alcohol was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water, washed with decyl alcohol, and purified by an amine-based modified silicone (NH DM1020: manufactured by Fuji Silysia) column chromatography (developing solution: toluene). After distilling off the solvent under reduced pressure, the obtained solid is recrystallized from a solvent mixture of decyl alcohol/ethyl acetate to obtain a compound represented by the formula (1-408), that is, 9-(ineryl)-7-based _5_ (3-7 hexyl-2-phenyl)phenyl)-7H-benzo[c]. Card saliva (〇 g g) 0 [Chem. 130] 171 201224109 38673pif

1H-NMR (500 MHz, CDC13): δ = 8.98 (d, 1H), 8 77 1H), 8.73 (d, 1H), 8.31 (t, 1H), 7.95 (m, 3H), 7.82 _ 7.72 W, 6H), 7.63 (d, 2H), 7.60 - 7,54 (m, 6H), 7.52 (d, 1H) 7 Λ 3H), 7.31-7.24 (m, 3H). ? &lt;(1-237) A synthetic example of the compound shown will be loaded with 9-(naphthalen-1-yl)-7-phenyl-5-(4,4,5,5-tetradecyl__13 dioxolane boron Alkan-2-yl)-7Η-benzo[c]carbazole (1.4g), conjugated bite (0.7 g), bis(dipyridinone) (〇) (0.2 g): JJ hexylphosphine (0.2 g), potassium phosphate (Κ3Ρ04) (4.1 g) and benzene (pseudoene) (9 ml) flask were stirred at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and water and toluene were added. After liquid separation, the solvent was removed under reduced pressure. The obtained solid was washed with decyl alcohol', further heated and washed with heptane, and then subjected to an amine-based modified tannin (NH DM1020: FuJ) Silysia) tube chromatography (developing solution: benzene/acetic acid B) The ester mixed solvent) was purified. At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. After distilling off the solvent under reduced pressure, the obtained solid was reprecipitated by adding 201224109 38673pif to obtain the formula (1-237) -([2,4,-linked" bite]_6-yl)-9-(naphthalene-1 - (〇.2g). The heat is dissolved in a stupid compound, and the compound represented by methanol is added, that is, the base is 7-phenyl-indole-benzo[c]-flavored saliva [131]

8&quot;

TfO

OTf

P

Ά oX, Pd(dpp〇CI2 T AcOK . , 0 , . CPME

Br

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 6=8.99 (d, 1H), 8.81 (d, 1H), 8.75 (d, 2H), 8.29 (m, 2H), 8.04 (d, 2H), 7.95 (t , 2H), 7.88 (m, 2H), 7.75 (m, 2H), 7.68 (d, 2H), 7.63 - 7.43 (m, 9H), 7.32 - 7.27 (m, 2H). &lt; a synthesis example of the compound represented by &gt; 173 201224109 38i) / 3pif will be cleaved with 9-(naphthalen-1-yl)-7phenyl-5-(4,4,5,5-tetradecyl-1, 3,2-dioxaborolan-2-yl)-7Η-benzo[c]carbazole (1.4 g), 6-bromo-2,2'-linked 0 ratio (0.7 g), Bis(dibenzylideneacetone) (〇) (0.2 g), tricyclohexylphosphine (0.2 g), potassium phosphate (K3P04) (4.1 g) and 1,2,4-trimercaptobenzene (pseudocumene) The (9 ml) flask was stirred at reflux temperature for 46 hours. The reaction solution was cooled to room temperature, and water and toluene were added to conduct liquid separation, and the solvent was evaporated under reduced pressure. The obtained solid was washed with decyl alcohol, and then purified by an amine-based modified phthalocyanine (NHDM1020: manufactured by Fuji Silysia) column chromatography (developing solution: toluene/ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. After distilling off the solvent under reduced pressure, the obtained solid is dissolved in toluene by heating, and methanol is added to reprecipitate to obtain a compound represented by the formula (1-189), that is, 5-([2,2·- linked. Acridine]-6-yl)-9-(naphthalen-1-yl)-7-phenyl-7H-benzo[c]carbazole (0.2 g). [化132]

S 174 201224109 38673pif

, L〇 p B-B: Pd(dppf)CI, AcOK

OTf

, CT

Pd(dba)2 Cy3P K3P04 CPME (/

1,2,4-trimethylbenzene

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): δ = 9.0 〇 (d, 1H), 8.81 (d, 1H), 8.71 (d, 1H), 8.63 (d, 1H), 8.37 (dd, 1H), 8.32 ( m, 2H), 7.95 (t, 2H), 7.91 - 7.84 (m, 3H), 7.75 (t, 1H), 7.68 (d, 2H), 7.63 - 7.44 (m, 9H), 7.34 - 7.27 (m, 3H). &lt;Synthesis Example of Compound represented by Formula (1-455)> 9-(naphthalen-2-yl)-7-phenyl-5-(4,4,5,5- Tetradecyl-1,3,2-dioxaborolan-2-yl)-7H-benzo[c]carbazole (1.4 g), 4-(3-bromophenyl)-pyridinium ( 0.7 g), bis(dibenzylideneacetone)palladium (〇) (〇.2 g), tricyclohexylphosphine (0.2 g), potassium phosphate (K3P04) (4.1 g) and 1,2,4-triterpene The benzene (pseudoene) (9 ml) flask was stirred at reflux temperature for 3 hours. 175 201224109.

______II After cooling the reaction solution to room temperature, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with water, and then washed with decyl alcohol, and then subjected to column chromatography (developing solution: benzene/ethyl acetate mixed solvent) by an amine-based modified silicone (NHDM1020: manufactured by FujiSilysia). purification. At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. After distilling off the solvent under reduced pressure, the obtained solid was dissolved in ethyl acetate by heating, and then re-precipitated by adding heptane to obtain a compound represented by the formula (1-455), that is, 9-(naphthalene-2-yl) -7-Phenyl-5-(3-(pyridin-4-yl)phenyl)-7H-benzo[c]. Card saliva (〇 1 g). φ [化133] ca β(〇Η)2

Pd(0Ac)2 TPP K3PO4

+ TfO OTf PA/THF

Pd(dba)2 Cy3P K3P04

9 U4-trimethylbenzene

s 176 201224109 38673pif The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13) ·· δ = 8.97 (d.1H)° 8 77 1H), 8.70 (dd, 2H), 8.05 (d, 1H), 7.99 (m, 1^/7.93^ 3m 7.89 (m, 1H), 7.80 - 7.74 (m, 3H), 7.71 (m, 1H), 7.68 - 7 60 (m, 6H), 7.59 - 7.49 (m, 7H), 7.45 (t, 1H) &lt; (1-59) Synthesis Example of Compounds Represented>

First of all, 'will be loaded with bis (trifluoromethane 7_phenyl I stupid [c sputum-5,9-diyl s (7_1 g), 3-acridine boric acid (I? g), sodium carbonate A flask of Pd(m3)4 (0.28 g), toluene (25 ml), ethanol (8), and water g (8 ml) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature. Adding an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and acetonitrile acetate to separate the liquid. The reduced pressure is determined by the solution of the mixture of the mixture by chromatography (extraction solution: benzene/ethyl acetate mixed solvent). Purification is carried out. At this time, the ratio of the acetic acid in the developing solution is gradually increased to elute the target. Thereafter, the solvent is distilled off under reduced pressure, and the obtained solid is washed with methanol, followed by ethanol. Crystallization, thereby obtaining 7-mercapto-9-(σ ratio -3-yl)-7H-benzo[c] misoester (3 $ g) of trifluorosulfonium sulfonate. The trifluorosulfonium sulfonate 7-phenyl_9-(.pyridin-3-yl)-7H-benzo[c]carbazole ester (3.〇g), 2-naphthaleneboronic acid (12 8 ), sodium carbonate (1_2§), 卩(^?113)4 (0.338), 甲笨(12 1111), ethanol (4 ml) and (4 ml) flask was stirred for 2 and a half hours under a nitrogen atmosphere at reflux temperature. The reaction solution was cooled to room temperature, and decyl alcohol was added thereto, and the precipitated solid was collected by suction filtration, and the solid was washed with water, followed by After cleaning with methanol, 'with amine-based modified silicone (NH DM1020 : Fuji 177 201224109 f

Purification by column chromatography (developing solution: toluene) was carried out by Silysia. After distilling off the solvent under reduced pressure, the obtained solid was washed with ethyl acetate to give the compound of formula (1-59), that is, 5-(naphthalen-2-yl)-7-phenyl-9 Bipyridin-3-yl)-7H-benzo[c]carbazole (1.9 g). [化134]

€^b(oh>2

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): δ = 8.97 (d, 1H), 8.79 (m, 1H), 8.75 (d, 1H), 8.68 (dd, 1H), 8.11 (m, 1H), 7.87 - 7.94 (m, 3H), 7.77 - 7..86 (m, 6H), 7.64 (m, 4H), 7.38 - 7.56 (m, 6H)) · &lt; Compounds represented by formula (1-10) Synthesis Example &gt; First, added in cyclopentyl methyl ether (CPME) (64 ml)

S 178 201224109 38673pif 2-(4-bromophenyl)pyridine (15 g) and pinacol borate (19.5 solution, add acetic acid under stirring at room temperature under nitrogen atmosphere (Pd(OAc) 2) (0.4 g), triphenylphosphine (PPh3) Q 5 g) and potassium acetate (AcOK) (1S.9 g). Thereafter, after stirring at reflux temperature for 2 hours, the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDU) (35 ml) and toluene (5 〇〇 ml) were added. The organic matter from which the salt has been removed by the water washing operation is obtained by the activated carbon tube column method (toluene), and 2 (4·(4,4,5,5_tetramethyl_u, 2_) is obtained. Dioxane pentane 1 yl) benzyl) pyridine (11.2 g). Next, in the case of 2_(4)(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)pyridine obtained as described above (6.9 Acid) 7-phenyl-7H- benzo[c]-salt 5,9-diyl vinegar (6 6 g) solution (3:1 by volume) (37 ml) under nitrogen atmosphere, To the warmth - add the acetic acid (4) g), triphenyl scale (4) g) and potassium silicate (Κ3Ρ04) (9.4 g). Thereafter, after mixing at reflux temperature, the reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid = DTA) (50 ml) and toluene (5, for example) were added. Purification of the organic substance from which the salt has been removed by a water washing operation by activated carbon column chromatography (toluene/ethyl acetate ratio)) to obtain a compound of the formula (M〇), which is a 7-phenyl group. 5,9_bisyl)phenylbenzin [c]carbazole (ι·2 g). [135] 179 5; 201224109 38673pif

Κ3Ρ°4 (1-10) THF/IPA(3/1) 7

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): δ = 8.97 (d, 1 Ή) 8 74 (m 3H), 8.11 (m, 5H), 7.76 (m, 9H), 7.54 (m, 6H), 7 47 (m) 2H) 7.45 (m, 1H), 7.35 - 7.23 (ra, 2H). Synthesis of a compound represented by the formula &lt;Formula (1-4) 彡 First, in cyclopentyl decyl ether (50 ml) Adding force σ has difluorinated, continuous acid): -Phenyl-7Η-benzo[c]吟峻_5,9-diyl vinegar (5 9g) and &amp; stilada ester (6.1 g) solution In the nitrogen atmosphere, at room temperature - surface stirring - surface addition MU, - bis (diphenyl scaly) ferrocene) two gas dish (11:

(0.41 g) and acetic acid unloading (5 9 g). Thereafter, after stirring for an hour at the reflux temperature, the reaction solution was cooled to room temperature, and water and ethyl acetate were added, such as a water washing operation. Next, methanol was added and the mixture was washed by heating. Thus, 7-stupyl·7H_benzo[Pursate] is used to obtain vinegar (5 g). Secondly, in the center of the fake boring (1,2,4_trimethyl stupid MU) === 7 7H_Benzene [Pak sitting 5,9_Secondary two two; = (four) (5.6g) In the solution, under the nitrogen 3 to the side of the dish, add one side to add a double (dipyridyl-propyl-bar ((

S 180 201224109 38673pif (Pd(dba)2 ) (0.6 g ), tricyclohexylphosphine (PCy3 ) (〇 6 g) and potassium phosphate (K3P04) (9.4 g). Thereafter, the mixture was stirred at 15 ° C for 5 hours, and then the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added thereto to carry out a water washing operation. The organic matter removed by the water washing operation was treated with a silica gel column (ethyl acetate), followed by activated alumina column chromatography (benzene/ethyl acetate = 9/1 (volume ratio) )) Purification. Further, heptane is added to the toluene solution to carry out reprecipitation, and the compound represented by the formula (1-4) is obtained, that is, 5,9_bis([2,2,_bipyrryl·5·yl)-7- Phenyl-7-benzo[c]n-carbazole (2.5 g). [化136]

P 9

Pd(dba>2 PCy3 K3P〇4 pseudocumene

(1-4) The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 9.02 (m, 1H), 8.98 (d 1H), 8.86 (m, 1H), 8.80 (d, 1H), 8.75 (m, 2H), 8.55 (d, 1H), 8-45 - 8.53 (m, 3H), 8.13 (dd, 1H), 8.00 - 8.08 (m, 2H), 7.75 -7.89 (m, 5H), 7.67 (m, 4H), 7.56 (m, 2H), 7.51 (t, 1H), 7.30 - 7.37 (m, 2H). &lt;Synthesis of a compound represented by the formula (1-744)&gt; in pseudocumene (1,2,4-trimium) Addition of 7_phenyl-7H-benzo[c]indole-5,9-diboronic acid vinegar (49 g) &amp; (o·mute base) 181 201224109 acridine (4.6 ml) In the solution of g), add palladium catalyst (Pd(PPh3)4) (〇.5 g) and potassium linnate (K3P04) (12g) of triphenylphosphine while stirring at room temperature under nitrogen atmosphere. ). Thereafter, the mixture was stirred at 160 ° C for 12 hours, and then the reaction liquid was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were washed with water. The organic matter from which the salt was removed by a water washing operation was purified by active oxidation column chromatography (曱本/乙乙乙为=4/6 (volume ratio)). Further recrystallization from toluene to obtain a compound represented by the formula (1-744), that is, 7-phenyl-5,9-bis(3-(pyridin-4-yl)phenyl)7H-benzo[c ]carbazole (3.5 g). [化137]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (5〇〇MHz, CDC13) : 5=8.89 (d, 1H), 8.77 (d, 1H), 8.69 (m, 4H), 8.01 (d, 1H), 7.92 (m, 1H), 7.80 (m, 2H), 7.69 - 7.77 (m, 4H), 7.50 - 7.67 (m, 14H), 7.47 (t, 1H). &lt;Synthesis Example of Compound represented by Formula (1-5)&gt; Addition of 7-phenyl-7H-benzo[c]carbazole-5,9-diborate (5_0 g) to pseudo-lye (1,2,4-trimercaptobenzene) (50 ml) In a solution of 5-bromo-2,3,-bin ratio (5.0 g), Pd(PPh3)4 (0.5 g) and potassium phosphate (12 g) were added while stirring at room temperature under a nitrogen atmosphere. Thereafter,

S 182 201224109 38673pif After mixing at 150 ° C for 20 hours, the reaction solution was cooled to room temperature aqueous solution, and the solid human in the liquid was collected by suction filtration to remove the mixed solvent of active oxidized toluene / ethyl ethoxide. ) to carry out purification. At this time, come to the exhibition ^ night. Learn the experiment into the Η (1) substance use method and separation and purification 7 machine-based = Division Publishing, page 94 method

The ratio of B I and B is gradually increased to dissolve the target. The recrystallization is carried out to obtain a compound represented by the formula (1): Γ = one ([2,3 hydrazinyl]-5 base)-7 phenyl-7 benzo[c]carbazole, [Chem. 138] g).

(1-5)

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (5〇〇MHz, CDC13): δ = 9.26 (m, 2H) 9 〇7 , 1H), 8.99 (d, 1H), 8.91 (m, 1H), 8.8G (d, 1H), 8.69 '(m 8.40 (m,2H),8·1〇(dd,1H),8.03 (d,1H), 7.99 (dd, im 7, (d,1H)' 7 84 (m,2H),7.76 ( m, 2H), 7.66 (m simplification 'eight 91 7.60 (m, 3H), 7, 45 (m, 2H). , &lt;synthetic example of the compound represented by the formula (1-20)&gt; Phenyl-7H-benzo[c]carbazole-5,9-diborate (5 1 )' is added to the olefin (1,2,4-trimethylbenzene) (50 ml) ,3·- 183 201224109 In a solution of bipyridine (4.6 g), Pd(PPh3)4 (0.5 g) and potassium phosphate (12 g) were added while stirring at room temperature under a nitrogen atmosphere. Thereafter, After stirring at 120 ° C for 5 hours, the reaction solution was cooled to room temperature, decyl alcohol was added, and the solid in the liquid was collected by suction filtration. The solid was washed with an aqueous solution of ethylenediaminetetraacetic acid (EDTA), followed by The water is washed, further washed with decyl alcohol, and further recrystallized from chlorobenzene to obtain a compound represented by the formula (1-20), that is, 5,9-bis([2,3'-bipyridyl]-6 -yl)-7-benzene -7H- benzo [c] carbazole (4.5g). [Of 139]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 9.34 (m, 1H), 9.29 (m, 1H), 9.00 (d, 1H), 8.80 (d, 1H), 8.66 (m, 2H), 8.40 - 8.48 (m, 2H), 8.26 (m, 3H), 7.93 (t, 1H), 7.79 - 7.89 (m, 4H), 7.75 (s, 1H), 7.65 - 7.72 (m, 5H), 7.61 (d, 1H ), 7.49 - 7.58 (m, 2H), 7, 37 - 7.45 (m, 2H). &lt;Synthesis Example of Compound represented by Formula (1-24) > In pseudocumene (1,2,4- Addition of 7-phenyl-7H-benzo[c]carbazole-5,9-diborate (5.0 g) and 5-bromo-3, in trimethyl benzene) (50 ml)

S 184 201224109 ^6〇/jpif in a solution of bismuth (5.0 g), Pd(PPh3)4 (12 g) and phosphoric acid (117 g) were added to the mixture at room temperature under nitrogen atmosphere. . Thereafter, at a reflux temperature of 1 M, the reaction solution was cooled to room temperature, and an aqueous solution of ethylamine tetraacetic acid (EDTA) and benzene were added for liquid separation. The decompression chamber is dissolved, and purified by (4) column chromatography (expansion liquid: benzene/acetic acid mixed solvent) to obtain a compound represented by the formula (1-24), that is, 5,9-di ([ 3,4'-ringpyridyl]_5_yl)_7_phenylindole•benzo(4)-oxazole (L〇g). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target. [化140]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): δ = 8.99 (m, 3H), 8.86 (m, 2H), 8.82 (d, 1H), 8.75 (m, 4H), 8.16 (m, 1H), 8.09 (m , 1H), 7-95 (d, 1H), 7.85 (t, 1H), 7.75 (dd, 1H), 7.63 - 7.72 (m, 5H), 7.51 _ 7.60 (m,7H). &lt; -634) Synthesis Example of Compound Illustrated &gt; Stage 1: Implanted with (4-nonoxynaphthalen-1-yl)boronic acid (43.1 g), 1,4·1 ali-methyl succinylbenzene ( 25.0 g), acid slant (182 g), Pd (PPh3) 4 185 201224109 38673pif (2.5g), pseudocumene (1,24_tridecylbenzene) (1000ml), tert-butanol (tBuOH) ( The flask of 200 ml) and water (40 ml) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and water and toluene were added for liquid separation, and the solvent was evaporated under reduced pressure to give 4,4,(2-nitrophenyl)bis(1-decyloxynaphthalene) (32.5 g). ). This crude product was used in the next step without purification. Stage 2: 4,442-nitro-1,4-phenylene)bis(1)methoxynaphthalene) (27.7 g) and triethyl phosphite (P(〇Et)3) (64 mi) The flask was stirred at 145 ° C for 1 hour. The reaction solution was cooled to room temperature, decyl alcohol was added, and the precipitated solid was collected by suction filtration. The solid was further washed with decyl alcohol to give 5-nonyloxy-9-(4-decyloxynaphthalen-1-yl)-7H-indole [c]. Sit (25.0 g). Stage 3: 5·曱oxy-9·(4-methoxynaphthalene)-7Η·benzo[c]carbazole (25.0 g), bromobenzene (11.7 g), bis ( Di-subunit acetone) palladium (0) (1.8§), [1,1,_biphenyl]_2-yldi-t-butylphosphine (2 2), potassium carbonate (25.7§) and pseudocumene The flask of (1,2,4-trimercaptobenzene) (25〇1111) was stirred at 155 Torr for 4 hours. The reaction solution was cooled to room temperature, and water and toluene were added to conduct liquid separation, and the solvent was evaporated under reduced pressure. The obtained solid was further washed with methanol to give 5-decyloxy-9-(4-decyloxynaphthalenyl)-7-phenyl-7H-benzod. Sit (23.0g). - Stage 4: 5-decyloxy-9-(4-decyloxynaphthalene)-ylphenyl-7H-benzo[c]carbazole (23.0 g) and pyridine hydrochloride ( The flask of 143 g) was mixed for 2 hours at 20 °C. The reaction solution was cooled to room temperature, and water was added for mixing, and the insoluble g] body was collected by suction filtration. Into 186 201224109 / jpif step The solid was washed with water to obtain 9-(4-hydroxynaphthalen-1-yl)-7-phenyl-7H-benzo[c]oxazol-5-ol (22.0 g). Stage 5: A flask containing 9-(4-hydroxynaphthalen-1-yl)-7-phenyl-7H-benzo[c]oxazol-5-ol (22.0 g) and pyridine (250 ml) was cooled in an ice bath Trifluoromethanesulfonic anhydride (TfOTf) (50.2 g) was added dropwise, and after completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour to complete the reaction. Thereafter, toluene and water were added to carry out liquid separation, and the organic layer was added. It was washed with 1 N hydrochloric acid, and then washed with sodium hydrogencarbonate. The solvent was evaporated under reduced pressure and purified by silica gel column chromatography (heptane / benzene = 9 / 1 (volume ratio)) with heptane. The solvent was distilled off under reduced pressure and the obtained solid was washed to give 4-(7-phenyl-5-((trifluoromethyl) Sulfo]yl)oxy)-7H-benzo[c]indazol-9-yl)naphthyl-1-acetate (23.1 g).

187 201224109 38673pif

MeO

8(OH)2

Me〇

MeO

OMe + Br

HO

TfOTf

Under a nitrogen atmosphere, the trifluoromethane 4-(7-phenyl-5-(((difluoromethyl)))))))嗤卡嗤冬基)naphthalene-1· vinegar (11.5g), 4"tt_acid (49g) two potassium (137 g; pi (m3)! (2-8g) ^ ^ mix 4 - (two 1) and The water (1Gml) flask was separated at reflux temperature. The solvent was decompressed and the solution was added to the chlorobenzene and the methanol was cleaned. Day and wealth. Under re-decompression, recrystallize the solid to obtain the formula. (4) The compound represented by the base (1·634), that is, 188 201224109 38673pif 7_bens-5-(°°° -4-yl)-9-(4-(n-r-sigma-4-yl)cai-1 _yl)-7Η·benzoquinone [c] carbazole (2.9 g).

+ (HO)2B-&lt;0N

Pd(PPh3)4 _K£2d_, mm, ZtBuOH/water

(1-634) The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 9.03 (d, 1H), 8.80 (d, 1H), 8.76 (m, 4H), 8.10 (m, 1H), 8.00 (d, 1H), 7.92 (m , 1H), 7.82 (t, 1H), 7.60 - 7.68 (m, 7H), 7.47 - 7.54 (m, 10H). &lt;Synthesis of a compound represented by the formula (1-743)&gt; There are 3-(3-bromo-p-phenyl)-specific bite (6.0 g), cyanoic acid ester (7.8 g), (l,l,-bis(diphenylphosphino)ferrocene) A flask of palladium chloride (H) (〇_6 g), potassium acetate (AcOK) (7.6 g) and cyclopentyl decyl ether (CPME) (52 ml) was stirred at reflux temperature for 3 hours. The reaction solution was cooled to warmness, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added and washed with toluene. The solid obtained by distilling off the solvent under reduced pressure was purified by activated carbon column chromatography (p-benzene) to obtain 3-(3-(4,4,5,5-tetradecyl-1 3 2- Dioxaborolan-2-yl)phenyl)acridine (6.0 g). ' ' ” Next, 3·(3·4,5,5_tetradecyl-1,3,2-dioxaborolan-2-yl) obtained as described above will be charged. Pyridyl) pyridine (4丨g), bis(trifluoromethane) acid 7-phenyl·7Η-benzo[Takaca _5,9_diyl g (3 8 g), phosphoric acid

189 201224109 386/ipif clock (2'7g)' Pd(PPh3)4 (〇.2g), pseudocumene (1,2,4_tridecylbenzene) ^13 ml), isopropanol (2·6 The flask of ml) and water (0.5 ml) was _ 6 trees at m degrees under nitrogen atmosphere. The reaction mixture was cooled to room temperature, and an aqueous solution of ethylamine tetraacetic acid (EDTA) was added to separate the mixture with toluene. The solid obtained by subjecting the solvent to a reduced pressure was purified by oxidizing column chromatography (developing liquid: toluene/acetic acid ethyl acetate). At this time, in the developing solution, the ratio of acetic acid to g is gradually increased to elute the target. Thereafter, recrystallization from gas benzene is carried out to obtain a compound represented by the formula (1743), that is, 7-phenyl-5,9-bis(3 octyl.3) phenyl)-7H-benzo[ c] 吟 〇 (〇·7 g ). [化143]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5=8.98 (d, 1H), 8.92 (d, 2H), 8.76 (d, 1H), 8.62 (m, 2H), 8.05 (d, 1H), 7.93 (m) , 2H), 7.87 (m, 1H), 7.45 - 7.81 (m, 17H), 7.38 (t, 2H). &lt;Synthesis Example of Compound represented by Formula (1-8710)&gt;

S 190 201224109 38673pif Stage 1: Under nitrogen, 38.6 g of bis-oxo-7H-benzo[c]carbazole, 1-fluoronaphthalene (38.8 g), cesium carbonate ( A flask of 90.6 g) and dimercaptopurine (DMSO) (460 ml) was heated and mixed at 145 ° C for 4 hours. After cooling the reaction liquid to room temperature, the salt was removed by suction filtration, and DMSO was evaporated under reduced pressure. After the obtained solid was washed with decyl alcohol, it was purified by hydrazine column chromatography (developing solution: heptane / benzene = 1 / 1 (volume ratio)) to obtain 5,9-dimethoxy- 7-(Naphthalene-1-yl)-7H-benzo[c]carbazole (32.5 g). Stage 2: Under a nitrogen atmosphere, 5,9-dimethoxy_7_(cai-1-yl)-7H-benzo[c]carbazole (42.5 g), pyridine hydrochloride ( (2) g) and N-methyl "pyrrolidone (NMP) (43 ml) flask at 2 Torr. (: heating and stirring for 1 and a half hours. The reaction solution was cooled to room temperature, and water and acetic acid 'ethyl ester were added for liquid separation. After distilling off the solvent under reduced pressure, the mixture was purified by a silica gel column to obtain 7- (naphthalen-1-yl)-711-benzo[〇;] ten-supplemented-5,9-diol (45 lv). Stage 3: under nitrogen atmosphere, will be loaded with 7·(Cai Xiaoji)_7H_ benzene And the flask of [〇]carbazole-5,9-diol (458) and pyridine (13〇1111) was cooled in an ice bath, and trifluorosulfonate anhydride (71.1 g) was added dropwise. After the dropwise addition, After stirring at room temperature for 16 hours, the reaction was completed, water was added, and the solid in the liquid was collected by filtration through pomelo gas. The obtained solid was mainly made up of decyl alcohol, and then chromatographed by Shixi rubber column (developing solution: 曱Benzene bis(difluoroanthracene), 7-(naphthalen-1-yl)-7H-stupid [C]D-carrionyl vinegar (63.2 g). , a soil 曰 [化144] 191 201224109

Η MeO

MeO

HO

...rolling milled r, 2~(4-(4,4,5,5-tetradecyl-1,3,2-dioxaborolane_2_) obtained as described above Phenyl)pyridinium (8.4 g), bis(trifluorosulfonium sulfonate) 7-(naphthalenyl)-7H-benzo[c]pyrene-5,9. monoester (6.4 g), Potassium phosphate (8.5 g), pd(pph3)4 (i) g), pseudocumene (1,2,4-trimethylbenzene) (75 ml), third butanol (5 ml) and water (1 = The flask was cooled to ≤ 1 G ^ at the temperature of the temperature. The reaction solution was cooled to a volume of (EDTA) aqueous solution and toluene, and the solvent was evaporated under reduced pressure, and the obtained solid was filtered while hot, and the mixture was filtered. Freshly in the gas, the crystal m is decomposed by deuteration, and the compound represented by re-base [59] is also known as 7-(naphthalene small) [sodium succinyl-2-yl) stupid base. Benzocaw (18g)e

S 192 201224109 38673pif

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): δ = 9.02 (d, 1H), 8,80 (d, 1H), 8.70 (m, 2H), 8.09 (m, 2H), 8.03 (m, 5H), 7.69 - 7.83 (m, l〇H), 7.55 (m, 3H), 7.48 (t, 1H), 7.39 (m, 1H), 7.30 . 7.38 (m, 2H), 7.23 (m, 2H), 7.18 (s , 1H). &lt;Synthesis Example of Compound represented by Formula (1-8711)&gt; First, bis(trifluorosulfoniumsulfonic acid) 7-(naphthalen-1-yl)-7H-benzo[ c] 咔. Sodium-5,9-dicarboxylate (6.4 g), pinacol borate (6.1 g), (i, 1 L bis(diphenylphosphino)ferrocene) dichloropalladium (II) (0.32 g The flask of potassium acetate (5.9 g) and cyclopentyl decyl ether (CPME) (50 ml) was stirred under a nitrogen atmosphere at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, and water and ethyl acetate were added to carry out a water washing operation, and then methanol was added thereto, followed by heating under reflux and stirring. Thus, 7-(naphthalen-1-yl)-7H-benzo[c]-salt-5,9-diborate (5.7 g) was obtained. Next, 'will be loaded with 7-(naphthalen-1-yl)-7H-benzo[Φcarbazino-5,9-diborate (5.2 g), 3-(4-) obtained as described above. Bromophenyl)pyridine (4.9 g), disc acid clock (9.2 g), Pd(PPh3)4 (0.50 g), winter tridecylbenzene (pseudocumene) (35 ml), tert-butanol ( 7 ml) and water (1.4 ml), bottle = nitrogen atmosphere, reflux temperature (four) 4 λ!, hour. The reaction solution was cooled to him, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added, and a solid was obtained by suctioning 193 201224109. Next, after washing with decyl alcohol, heating was carried out by adding a gas, and the unnecessary components were separated by filtration by suction filtration. Thereafter, the solvent is distilled off under reduced pressure, and recrystallized from gas benzene to obtain a compound represented by formula (1_8711), that is, 7·(naphthalen-1-yl)-5,9-bis (4-(pyridyl) 3-yl)phenyl)-7H-benzo[c]indole (4.4 g). [化146]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 6 = 9.03 (d, 1H), 8.87 (m, 2H), 8.81 (d, 1H), 8.09 (t, 2H), 8.03 (d, 1H), 7.67 - 7.93 (m: 9H) 7.46 - 7.65 (m, 9H), 7.27 - 7.39 (m, 5H), 7.17 (s, iH) &lt;Synthesis of a compound represented by formula (1-8712)&gt; There are 7·(naphthalene-1·yl HH- benzo[c]carbazole·5,9-dioxalate (4.8 g), 4-(4-bromophenyl)acridine (4.5 g), Potassium phosphate (85 g), Pd(PPh3)4 (〇.46g), 1,2,4-trimethylbenzene (pseudocumene) (3〇ml), third butanol (6ml) and water ( The flask of 1.2 ml) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, an aqueous solution of ethylenediaminetetraacetic acid (EDTA) was added, and a solid was obtained by suction filtration. Secondly, by methanol After washing, 'chlorinated benzene is added and heated, and the unnecessary components are separated by filtration by suction filtration. Thereafter, the solvent is distilled off under reduced pressure, and recrystallized from the gas 201224109 38673pif to obtain the formula (1-8712). a compound, i.e., 7-(naphthalen-1-yl)-5,9-bis(4-(acridin-4-yl)phenyl)-7H-benzo[c]carbazole (3.5 g). 147]

Pd(PPh3)4 K3P〇4 pseudocumene, /t-BU〇H/water

(1-8712) The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 9.03 (d, 1H), 8.81 (d, !Η), 8.66 (m, 4H), 8.11 (d, 1H), 8.05 (t, 2H), 7.83 ( t, 1H), 7.65 - 7.80 (m, 9H) 7.49 - 7.59 (m, 8H), 7.36 (m, 2H), 7.29 (m, 1H), 7.16 (s, 1H). &lt; Synthesis example of the compound represented by bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-monoester (7.3 g), 2 A flask of acridine-zinc bromide 0.5 M-THF solution (50 ml) and Pd(pph3) 4 (0.96 g) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (Η〇τα) and ethyl acetate were added to conduct liquid separation. The organic layer was further washed with saturated water, and the solvent was removed under reduced pressure. Next, purification is carried out by means of Shixi gum chromatography (developing solution: ethyl acetate / benzene = 1 / 20 (volume ratio)), and further recrystallized from benzene to obtain a compound represented by the formula, that is, 7 _Phenyl·5,9-bis(acridin-2-yl)-7H-benzo[c]carbazole 195 201224109 ^δθ/^pif (1.2 g). [化148]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 8.97 (d, 1H), 8.79 (m, 1H), 8.76 (d, 1H), 8.70 (m, 1H), 8.15 (m, 2H), 8.08 (dd , 1H), 7.73 - 7.84 (m, 4H) 7.58 - 7.68 (m, 6H), 7.46 - 7.55 (m, 2H), 7.33 (m, 1H), 7.21 (m, 1H). &lt; 2) Synthesis example of the compound represented by bis(trifluoromethanesulfonic acid) 7-phenyl-7H-benzo[c]carbazole-5,9-diester (5.9 g), a flask of 3-pyridineboronic acid (2.5 g), sodium carbonate (4.0 g), Pd(PPh3)4 (0.5 g), toluene (40 ml), ethanol (12 ml) and water (12 ml) under a nitrogen atmosphere at reflux temperature Stir under 2 hours. The reaction solution was cooled to room temperature, and saturated aqueous sodium chloride and ethyl acetate were added for liquid separation. The solid obtained by distilling off the solvent under reduced pressure was purified by silica gel chromatography (developing solvent: benzene/ethyl acetate = 18 (volume ratio)), followed by recrystallization from heptane and further recrystallization from ethanol. To obtain a compound represented by the formula (1-2), that is, 7-phenyl-5,9-bis(pyridin-3-yl)-7H-benzo[c]carbazole (2.1 g) 〇 ] 201224109 38673pif

P

^^~B(〇H)2 Pd(PPh3): N 32^^3 Toluene /EtOH/water

(1-2)

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): δ = 9.〇6 (m, 2H), 8.77 (m, 2H), 8.69 (m, 1H), 8.59 (m, 1H), 7.97 (m? m), 7.93 (d, 1H) 7-86 (m, m) 7.81 (t, 1H), 7.61 - 7.71 (m, 6H), 7.56 (t, IH) 7-49 (m, 2H), 7.43 (m, 1H) ), 7.38 (m, 1H). 'Synthesis of a compound represented by the formula (1-541)> First, a bis(trifluoromethanesulfonate phenyl-711-benzo(4) fluorene is charged. Salivation _5,9-diyl g (Μ.7 g), 2_ silkworm Q 5 m_thf solution (5〇mi).pd(PPh3)4(〇.87g)^THF(5〇ml) ^^ Under nitrogen atmosphere, at reflux temperature _ 3 hours. The anti-ship is cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate are added to carry out the / knife solution. The organic layer is further processed with saturated brine. Washing, decompression and solvent removal. Secondly, by using Shixi gum chromatography (expansion liquid: ethyl acetate / toluene = : 〇丄 volume ί)), the purification is carried out, and the step is further recrystallized from ethanol. Difluorodoped 7·phenyl_9 phase 9 Yueyang·Benzene fine saliva _5· 基酉(5.1 g). Next, the boric acid (1.3 g) obtained as described above, which is obtained by the above-mentioned method, can be used as the above-mentioned boric acid (1.3 g). A flask of sodium carbonate (12 g) pd (p oxime toluene (1) ml), ethanol (4 ml) and water (4 mi) was placed on a gas ring 197 201224109. A V v , 袅 t 乙 乙 崎 _ _ 15 hours. The reaction rr__EDTA) aqueous solution and acetic acid are subjected to f屯toluene/acetic acid acetylation of the obtained solid at this time, so that the acetic acid in the developing solution is increased to elute the target. Thereafter, the solid obtained by the acetic acid Γ匕=agent is washed to obtain the formula (1)41).

"17_本基钟岭2_基)5 (4 (bite 2 bases > benzo[CHn sits (0.4g). ^ [化150]

〇-:

ZnBr 2-0 ratio biting base THF zinc bromide (Π) b(oh)2

Pd(PPh山 Νθ2〇〇3 曱‘Stupid 3

/Ettii/water (1-541) The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 8.97 (d, 1H), 8.80 (m? 1H), 8.75 (d, 1H), 8.72 (m, 1H), 8.15 (d, 1H), 8.10 (d , 2H), 7.73 - 7.83 (m, 8H), 7.63 - 7.70 (m, 5H), 7.61 (d, 1H), 7.53 K 1H), 7.49 (t, 1H), 7.33 (m5 1H)? 7.23 (m , 1H). &lt;Synthesis Example of Compound represented by Formula (1-564)&gt;

S 198 201224109 38673pif under nitrogen atmosphere will be charged with 4-(7-phenyl_5_(((trifluoromethyl)) fluorenyl)HH-benzo[C]carbazole Base naphthalene·丨·^ vinegar (^ g), 2-pyridyl zinc bromide 5.5 m〇l/l THF solution (5 〇ml) and Pd(PPh3)4 (0.25 g) flask in reflux The mixture was stirred for 3 hours at a temperature. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTa) and ethyl acetate were added for liquid separation. The solvent was distilled off under reduced pressure, and the residue was purified by aq. Purification of the obtained solid by the method (developing solution, hydrazine/acetic acid-acetic acid mixed solvent), followed by purification by gel column chromatography (developing solution: toluene/ethyl acetate mixed solvent) to obtain the formula (^64) The compound represented by '7-phenyl-5-(α ratio β-but-2-yl)-9·(4-πbiti-2-yl)-indenyl)-7Η-benzo[ c] carbazole (〇.4 g). In this case, any of the chromatographic methods is such that the ratio of ethyl acetate in the developing solution is gradually increased to elute the target. [化151]

(1-564) The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 6 = 9.01 (d, 1H), 8.80 (m 3H), 8.16 (m, 2H), 8.09 (d, 1H), 7.77 · 7.86 (d, 3H), 7.72 ( s' 1H), 7.57 - 7.67 (m, 10H), 7.43 - 7.53 (m, 4H), 7.35 2^^ <Synthesis of compound represented by formula (1-575)> First, it will be loaded with double (7-phenyl-7H_benzoxazole trifluoromethanesulfonate 199 201224109 ^δθ/jpif -5,9-di-ester (5.9g), 3-pyridine boronic acid d.4g), sodium carbonate (21) ,

A flask of Pd(PPh3)4 (0.23 g), toluene (21 ml), ethanol (7 ml) and water (7 ml) was stirred under a nitrogen atmosphere at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and ethyl acetate were added for liquid separation. The solvent was evaporated under reduced pressure, and purified by EtOAc EtOAc (EtOAc:EtOAc:EtOAc At this time, the ratio of the acetic acid B of the developing liquid towel was gradually increased to dissolve the target material. Thereafter, 'minus_desolved solvent, the solid obtained is washed with methanol'. It is recrystallized by a solution to obtain three 1? 7 7-phenyl winter (. than bit -3- group) - 7H - stupid [c] Ten-seat ester (2 5 g). Next, the three-gas catalyzed acid 7-stupyl group obtained as described above is loaded with the above-mentioned (4) (1.3 g), (4 lycopene-2-yl) ) 2) Acid (丨'3 g), sodium carbonate (12 g), Pd (PPh3) 4 (0.31 g), benzene (12:1) ethanol (4 m hydrazine and water (4 flask in nitrogen ring) +Brothers, back to the temperature _ 15 hours. The reaction solution was cooled to room temperature, 2 acetic acid (EDTA) aqueous solution and toluene were separated. The organic layer was washed with water and the solvent was removed under reduced pressure. The German, the poor, the 隹-$ first, followed by the ethyl acetate to wash 7! Recrystallized, to obtain the compound azole (ug) represented by the formula (1_575). Base) base) outside the bite winter base HH -Benzene[φ卡[化152] 2〇〇

S 9 201224109 38673pif

TfO

Pd(PPh3)4ΡΓ3 /EtOH/water

Pd(PPh3)4 Ν32〇〇3 toluene u /EtOH/water

(1-575)

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): δ=8·98 (d, 1H), 8.79 (m, 1H), 8.71 - 8.76 (m, 2H), 8.69 (m, 1H), 8.10 ( d, 2H), 7.93 (d, 1H), 7.87 (dt, 1H) 7.75 - 7.82 (m, 7H), 7.63 - 7.69 (m, 43⁄4 7.55 (m, 1H), 7.49 (m, 2H), 7.43 ( m, 1H), 7.23 (m, 1H). Synthesis of a compound represented by hydrazine (1-599) &gt; ^ Under a nitrogen atmosphere, 4-(7-phenyl-)-trifluorosulfonate 5((((Trifluoromethyl))) oxy) _7 Η benzo[c] guanidinyl) naphthalenyl ester (3^ ', ^ pyridine boron, (1-6 g) phosphoric acid A flask of potassium (3·6 g) 'Pd(PPh3)4 (〇, 25 μL of ethoxylated oxime (18 ml) and water (3.6 ml) was returned, and the dish was stirred for another 12 hours. The reaction solution was cooled. Tetraacetic acid (EDTA, 7 丨 至 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到 到7 ^ 仃 Purification 'Get the base represented by formula (1_599)) _7H-benzo[e(tetra)- s-lingling 3-yl)naphthalene-h 酉曰 ratio is slowly increased - the target is dissolved. 201224109 38673pif [Chem. 153]

TfO

/water

Pd(PPh3)4 Shen Ki·Ethylene

(1-599) The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 9.03 (d, 1H), 8.80 (m 3H), 8.70 (m, 2H), 8.10 (m, 1H), 7.96 (d, 1H), 7·89 ( m, 3H)' 7.82 (t, 1H), 7.58 - 7.67 (m, 7H), 7.43 - 7.54 (tn, 8H). ' Synthesis of compounds represented by formula (1·742)&gt; Adding 7·phenyl-7H-benzo[c]carbazole_59-diborate (5〇g) and 2 to pseudocumene (1,2,4-trimethylbenzene) (50 ml) (3_Bromophenyl) ° Compared to the bite (4.7 g) solution, add Pd(pPh3)4 (3·6 g) and potassium phosphate (11.7 g) while stirring at room temperature under nitrogen atmosphere. . Thereafter, after 16 hours at the reflux temperature, the reaction solution was cooled to room temperature, and an aqueous solution of ethylenediaminetetraacetic acid (EDTA) and benzene were added for liquid separation. After depressurization = solvent removal, purification was carried out by silica gel column chromatography (developing solution: hydrazine/acetic acid vinegar mixed t = agent). At this time, the ratio of the acetic acid in the developing solution is gradually increased to elute the target. Further, the coloring component is removed by an activated carbon column (expansion liquid toluene) to obtain a formula (1-742).

202 S 201224109 38673pif The compound 'i.e., 7-phenyl-5,9-bis(3-(°.din-2-yl)phenyl)-7H_benzo[c]carbazole (0.5 g). [化154]

The structure of the obtained compound was confirmed by NMR measurement. 1H-NMR (500 MHz, CDC13): 5 = 8.96 (d, 1H), 8.69 -8-77 (m, 3Η), 8.29 (m, 1H), 8.12 (m, 1H), 8.08 (m, 1H) , 8.02 (m, 1H), 7.97 (m, 1H), 7.71 - 7.81 (m, 7H), 7.54 - 7.66 (m, 7H), 7.50 (m, 1H), 7.45 (t, 1H), 7.25 (m , 2H).

The other derivative compound of the present invention can be synthesized by appropriately changing the starting compound and using the method of the above synthesis example. Further, the compound of the present invention also contains at least a part of hydrogen atoms which are substituted by hydrazine. The compound can be synthesized in the same manner as described above by using a raw material which is deuterated at a desired position. Hereinafter, the examples are exemplified to explain the present invention in more detail, but the present invention is not limited to the examples. &lt;Example 1 and Comparative Example 5&gt; The electroluminescent elements of Example 1 and Comparative Example 5 were produced, and the driving start voltage (V) of the constant current driving test and the time of maintaining the brightness of the initial brightness of 80% or more were measured ( dagger). Hereinafter, examples and comparative examples will be described in detail.

S 203 201224109 38673pif The material composition of each of the electroluminescent elements of Example 1 and Comparative Example 5 produced is shown in Table 1 below. [Table 1] Hole injection layer Hole transport layer Light-emitting layer Electron transport layer Host dopant Example 1 CuPc NPD Compound compound Compound (A) (B) (1-335) Comparative Example 5 CuPc NPD Compound Compound (A) (B) (C) In Table 1, "CuPc" is copper phthalocyanine, "NPD" is Ν, Ν·-diphenyl-fluorene, Ν'-dinaphthyl-4,4'-diamine linkage Benzene, the compound (Α) is 9-phenyl-10-[6-(1,Γ; 3,Γ)bitriphenyl-5'-yl]naphthalen-2-ylindole, and the compound (Β) is N5, N5 , N9, N9-7,7-hexaphenyl-7H-benzo[c]indole-5,9-diamine, compound (C) is 5,5'-(2-phenylindole-9,10- Dikibium)di-2,2'-bipyridine has the following chemical structures, respectively. [化155]

204 S 201224109 38673pif

&lt;Example 1&gt;&lt;Component of using compound (1-335) in electron transport layer&gt; ITO of iridium having a thickness of 180 nm by iridium plating to 150 mm and 26 mm x 28 mm x 〇.7 A glass substrate of mm (manufactured by 〇pt〇 Science, Ine.) was used as a transparent supporting substrate. The transparent support substrate is placed on the right side of the vacuum-manufactured company (manufactured by Vacuum Machinery Co., Ltd.), and the person who has the CuPe is used to make a steamed money boat, and the boat for vapor deposition is installed, and the compound (A) is charged. Molybdenum lyo plating boat 1 person has compound (8) indium test boat, | 205 201224109 38673pif Indium hydride steamed into the formula (1·335) And the person who loaded the Yang (4) steaming mine boat on the transparent support floor substrate "ΙΤ0 m successively formed the following layers of vacancies decompression to 5x10-4 Pa, first heat the cuPc loaded with sputum, steamed to a film thickness 10 〇 nm to form a hole for injection 2. Use a boat filled with NPD for heating, and steam the money to form a film thickness to form a hole transport layer. Next, a compound (A boat was placed in a boat with a steaming shovel containing the compound (8) and vapor-deposited to a film thickness of 35 nm to form a light-emitting layer. The weight of the compound person (Β) was #比比It is about 95 to 5 to adjust the speed of the two-dimensional Γΐ ϊΐ ϊΐ ; ; ; 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 335 /see~1 nm/see. 0 003 / After the steaming of the lithium is evaporated, the boat is heated to a film thickness of 苴 = 蒸 卿 卿 卿 卿 卿 卿 卿 ' ' ' ' ' ' ' ' ' ' ' ' ' ' The organic electroluminescent device was obtained by forming a cathode at a vapor deposition rate of _rnn/sec to 1Gnm/see. When the ITO electrode is used as the anode and the DC voltage is applied as the step of the Dunhua_Lu electrode, the wavelength is about 455 nm, and the current density of 2000 cd/m2 is obtained by borrowing the gas to carry out the strange current driving test. . _ The initial f pressure of the test is 61G V, and the time to maintain the brightness above 80% (1600 cd/m2) is the time of 206 201224109 38673pif. &lt;Comparative Example 5&gt;

An organic EL device was obtained in the same manner as in Example 1 except that the compound represented by the formula (1-335) was replaced by the compound (c). The ITO electrode was used as the anode. The lithium fluoride/aluminum electrode was used as the cathode, and a constant current driving test was carried out by using a current density of 2000 Cd/m2 to obtain an initial luminance. The driving test starting voltage was 4.78 V, and the time for maintaining the brightness of 8 % or more of the initial value was 39 hours. The above results are summarized in Table 2. [Table 2] The electron transport layer maintains brightness of 80% or more of the initial luminance - (h) B Example 1 Compound (1-335) 600 Comparative Example 5 Compound (C) 39 Starting voltage (V) <Bee example 2~ Example 11 and Comparative Example 6 and Comparative Example 7 The light-emitting elements of Example 2 to Example 11 and Comparative Example 6 and Comparative Example 7 were produced, and the driving start (V) of the constant current driving test was measured, and the initial brightness was maintained. The time (^) of the brightness of more than 80%. (Examples and comparative examples thereof will be described in detail. The material composition of each of the examples 2 to n and the comparative example 6 and the comparative electroluminescent element produced is as shown in the following Table 3. 207 201224109 38673pif [Table 3] Hole injection layer hole transport layer, photo layer electron transport layer host dopant Example 2 HI NPD Compound (E) Compound (B) Compound (1-140) Example 3 HI NPD Compound (E) Compound ( B) Compound (1-212) Example 4 HI NPD Compound (E) Compound (B) Compound (1-431) Example 5 HI NPD Compound (E) Compound (B) Compound (1-383) Example 6 HI NPD Compound ( E) Compound (B) Compound (1-384) Example 7 HI NPD Compound (E) Compound (B) Compound (1-376) Example 8 HI NPD Compound (E) Compound (B) Compound (1-360) Example 9 HI NPD Compound (8) Compound (B) Compound (1-335) Example 10 HI NPD Compound (E) Compound (B) Compound (1-237) Example 11 HI NPD Compound (E) Compound (B) Compound (1-59) Comparative Example 6 HI NPD Compound (E) Compound (B) Compound (6) Comparative Example 7 HI NPD Compound (E) Compound (B) Compound (H) In Table 3, "HI" is N4, N4'-diphenyl-N4, N4'-bis(9-phenyl-9H-carbazol-3-yl) )-[1, fluorene-biphenyl]-4,4'-diamine, compound (E) is 9-phenyl-10-(4-phenylnaphthalen-1-yl)anthracene, and compound (G) is 2 , 7-bis([2,4'-biacridinyl]-6-yl)-9-phenyl-9-indole, the compound (Η) is 3-(3-(10-(naphthalen-2-yl)蒽-9-yl)phenyl)pyridine, and "Liq" is lithium quinolate. The chemical structure is as follows.

208

S 201224109 38673pif [化156]

&lt;Example 2&gt; Element for using compound (Ul4〇) in % 鞠 鞠 layer> The 〇 咖 咖 咖 将 〇 〇 〇 〇 〇 〇 〇 〇 〇 180 180 咖 咖 咖 咖 咖 咖 咖 咖 咖The glass substrate (7) suppresses the mosquito plate. (4) _ support substrate; commercially available d money (Showa vacuum limited finite substrate holder on the 'supplied into the skirt of the m illusion of the NPD reversing evaporation boat, loaded with compounds;;: full J = Mine boat, remanufactured vapor-filled dish filled with compound (B), ^ 209 201224109 J80/3pif Compound represented by formula (1-140) (4) Steamed ore dish (4) Steamed boat Filled with a steamed boat with a crane in the town. #题入银的π:!= The following layers are formed on the enamel film of the substrate. The true 4 is reduced to 5x1 (MPa, first loaded Steaming of m = order heating, vapor deposition is 4 〇nm thick to form a hole injection layer ', and then steaming the boat to heat, vapor deposition to a film thickness of 25 (10)

Next, the steamed material charged with the compound (Ε) was simultaneously heated by vapor deposition of a vapor deposition vessel having a thickness of 25 ° (8), and the thickness of the film was 25 nm to form a light-emitting layer. The steaming speed was adjusted so that the weight ratio of the compound (?) to the compound Β) became about % to 5.隹2 2 is equipped with a compound represented by the formula (M4G). The boat is used to form an electron transport layer by vapor deposition at a film thickness of 2 〇 nm. The plating rate of each layer is 0.01 nm/sec to 1 nm/sec.

After, the sub-loaded with Liq's Luo forging boat for heating, steamed at a deposition rate of nm.1 nm/sec~〇.1 nm/sec, and then recorded as a film thickness, followed by The boat of magnesium and the boat with silver are simultaneously heated and recorded as film thickness UK) nm. At this time, the ratio of the atomic ratio of _ to silver was changed to 10 &amp; 1 to adjust the vapor deposition rate, and the cathode was formed so that the vapor deposition rate was 0.1 nm to 1 Ornn to obtain an organic electroluminescence device. The ITO electrode was used as an anode, and the magnesium/silver electrode was used as a cathode. When a direct current voltage was applied, blue light having a wavelength of about about nm was obtained. Moreover, by performing the calibration current drive test with a current density of 2 〇〇() ed/m2 to obtain the initial immunity, the 'axis test voltage is 5.21 V, keeping the initial

S 210 201224109 38673pif The brightness of 80% (1600 cd/m2) or more of brightness is 24 hours. &lt;Example 3&gt;&lt;Element of Compound (1_212) used in the electron transport layer> Compound (1-140) was replaced with Compound (丨-212), and the method based on Example 2 was used. An organic EL element was obtained. The IT 〇 electrode was used as the anode and the magnesium/silver electrode was used as the cathode, and the strange current drive test was carried out by using the current enthalpy of 2000 cd/m 2 to obtain the initial redundancy. The drive test start voltage is 3.31 V, and the time to maintain the brightness above 8〇% of the initial brightness is 107 hours. ~ &lt;Example 4&gt;&lt;Component using compound in electron transport layer&gt; Compound (1-140) was replaced with compound (1-431), and otherwise obtained by the method based on Example 2 Organic EL element. A constant current driving test was carried out by using a Ιτ〇 electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 Cd/m2. ^ φ The starting voltage of the test is 4.79 V, and the time to maintain the brightness of 8初始% or more of the initial brightness is 445 hours. &lt;Example 5&gt;&lt;Component using compound (1-383) in the electron transport layer&gt; ^Compound compound (Μ40) was replaced with compound (1-383), and otherwise based on Example 2 An organic EL element was obtained by the method. Ipτ〇, the pole is used as the anode, and the slit/silver f-pole is used as the cathode, and (iv) is used to obtain the current density of the initial acceptance of 2_ed/m2*. The starting voltage of the driving test is 6.37 V, which keeps the brightness of the initial brightness above 8〇%.

211 S 201224109 38673pif The time is 379 hours. &lt;Example 6&gt;&lt;Component using compound (U84) in electron transport layer&gt; Compound (1-140) was replaced with compound (1384), and otherwise obtained by the method based on Example 2 Organic EL element. A constant current driving test was carried out by using an IT crucible as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial shell of 2000 cd/m2. The driving test starting voltage was 6.20 V, and the time to maintain the brightness of 8 % or more of the initial brightness was 258 hours. &lt;Example 7&gt;&lt;Component using compound (1_376) in the electron transport layer&gt; Compound (1-140) was replaced with compound (u%), and the method based on Example 2 was used. An organic EL element was obtained. A constant current driving test was carried out by using an IT crucible as an anode and a magnesium/silver electrode as a cathode to obtain a current density of 2,000 degrees Cd/m2 at an initial π degree. The driving test starting voltage was 6.74 V, and the time to maintain the brightness of 8 〇% or more of the initial brightness was 2 〇〇 hours. &lt;Example 8&gt;&lt;Use of element (1-360) in the electron transport layer&gt; ▲Compound compound (1-140) was replaced with compound (1_36〇), except by Example 2 An organic EL element was obtained by a standard method. A constant current driving test was carried out by using an IT crucible as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial redundancy of 2000 Cd/m2. The starting voltage of the driving test is 5.64 V, which keeps the brightness of the initial brightness above 8〇%.

S 212 201224109 38673pif The time is 352 hours. &lt;Example 9&gt;&lt;Component using compound (1-335) in electron transport layer&gt; Compound (1-140) was replaced with compound (35), and otherwise based on Example 2 An organic EL element was obtained by the method. The IT crucible electrode was used as an anode and the town/silver electrode was used as a cathode, and a constant current driving test was carried out by using a current density of an initial redundancy of 2000 cd/m2. The driving time of the driving test was 7.25 V ', and the time to maintain the brightness of 8 % or more of the initial brightness was 289 hours. &lt;Example 10&gt; <Elements using Compound (1_237) in Electron Transport Layer> Compound (1-140) was replaced with Compound (ι_237), and otherwise obtained by the method based on Example 2 EL component. A constant current driving test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial redundancy of 2000 cd/m2. The driving voltage of the driving test was 4.75 V, and the time to maintain the brightness of 8初始% or more of the initial brightness was 480 hours. &lt;Example 11&gt;&lt;Component using compound (1-59) in the electron transport layer&gt; Compound (1-140) was replaced with compound (Bu 59), and otherwise based on Example 2 An organic EL element was obtained by the method. A constant current driving test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of 2000 Cd/m2 of initial twist. The driving test starting voltage is 5.28 V, which keeps the initial brightness above 8〇%. II: 1 213 201224109 The 38673 pif time is 275 hours. &lt;Comparative Example 6&gt; An organic &amp; element was obtained by the method of the compound (6), and the method based on Example 2 was used. Ting = 乍 as the anode, 赖 / silver electrode as the cathode, by using

A constant current crane test was carried out by compiling the cake density. The result of the drive test was 3.86 V, and the brightness of the brightness above 8〇% of her brightness was 114 hours. &lt;Comparative Example 7&gt; An organic EL device was obtained by the method of Example 2 except that the compound (1-14G) was replaced with the compound (Η). A constant current driving test was carried out by using an ιτ〇 electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 Cd/m2. As a result, the driving test starting voltage was 3.91 V, and the initial brightness was maintained at 8 〇 &amp; The above results are summarized in Table 4.

S 214 201224109 joo/jpif [Table 4]

<Reference Example 1 to Reference Example 3 and Comparative Example m, t匕 Comparative Example 2> Preparation of Reference Example 1 to Reference Example 3 and comparison of the m and t elements of Comparative Example 2 and tb, and (4) The time at which the starting voltage () and the brightness of the initial shell degree are maintained at 80% or more (h&gt; is described in detail with reference to the reference examples and comparative examples thereof. Reference Example 1 to Reference Phase 3 and its tb Comparative Example The material composition of each layer in the electroluminescent device of Comparative Example 2 is as shown in the following Table S. 215 201224109 38673pif [Table 5] Hole injection layer hole transport layer Light-emitting layer Electron transport layer host dopant Reference Example 1 CuPc NPD Compound (A) Compound (Β) Compound (1-10) Reference Example 2 CuPc NPD Compound (A) Compound (Β) Compound (1-4) Reference Example 3 CuPc NPD Compound (A) Compound (Β) Compound ( 1-744) Comparative Example 1 CuPc NPD Compound (A) Compound (Β) Compound (C) Comparative Example 2 CuPc NPD Compound (A) Compound (Β) Compound (D) In Table 5, "CuPc" is copper phthalocyanine "NPD" is N,N'-diphenyl-fluorene, Ν'-dinaphthyl-4,4'-diaminobiphenyl, and the compound (Α) is 9-phenyl-1. 0-[6-(1,Γ; 3,Γ)bitriphenyl-5'-yl]naphthalen-2-ylindole, the compound (Β) is Ν5, Ν5, Ν9, Ν9-7,7-hexaphenyl -7Η-benzo[c]indole-5,9-diamine, compound (C) is 5,5·-(2-phenylindole-9,10-diyl)di-2,2'-linked fluorene The pyridine and the compound (D) are 2-phenyl-9,10-bis[4-(2-pyridyl)phenyl]phosphine having the following chemical structures, respectively. [Chem. 157] 201224109 38673pif

CuPc

&lt;Reference Example 1&gt; Element for using compound (LW) in the sub-transport layer&gt; The yttrium plated film having a thickness of 18 G nm was ground to 15 〇 = 26 mm mm of mm. The ugly glass substrate (〇pt〇c, manufactured by Ine·) is used as a transparent branch plate. The phase-supporting substrate is fixed on a commercially available new device (the real line of the Guardian Co., Ltd.), and the molybdenum-made vapor-deposited vessel with the CuPe is placed in the slab. There are compounds: a steaming clock, a boat, and a compound (8), which is made by steaming _ boat, ^ 217 201224109 38673pif a molybdenum vapor deposition boat containing a compound represented by the formula (MO), and lithium fluoride charged therein. The molybdenum vapor deposition boat and the aluminum-plated tungsten vapor deposition boat JHL are sequentially formed on the ITO film of the transparent support substrate to form the following layers. The vacuum chamber is depressurized to 5XHM Pa 'first loaded In the case of CuPc, it is heated by a boat, and the steaming key is a film thickness of 100 nm to form a hole injection layer. Next, the boat for vapor deposition in which NPD is charged is heated, and the film thickness is formed by vapor deposition to form a hole. Next, the vapor deposition boat in which the compound (A) was placed and the vapor deposition boat in which the compound (B) was placed were simultaneously heated: • The film was deposited to have a film thickness of 35 nm to form a light-emitting layer. The evaporation rate is adjusted in such a manner that the weight ratio of the compound (A) to the ruthenium complex (B) becomes about 95 to 5. The steaming vessel filled with the compound represented by the formula (1-10) was heated and vapor-deposited to a film thickness of 15 nm to form an electron transport layer. The steaming speed of each layer was 0.01 nm/sec. After that, the vapor deposition boat loaded with lithium fluoride is heated and vapor-deposited at a deposition rate of 0.003 nm/sec to 0.1 nm/sec to a film thickness of nm5 nm, followed by loading. The boat for vapor deposition of aluminum was heated and vapor-deposited at a vapor deposition rate of φ nm/sec to 10 nm/Sec to a thickness of 1 〇〇 nm, thereby forming a cathode to obtain an organic electroluminescence element. The ITO electrode serves as an anode, and the fluorinated electrode is used as a cathode. When a direct current voltage is applied, a blue light having a wavelength of about 455 nm is obtained, and is implemented by using a current density of an initial luminance of 2 ed/m 2 . Constant current drive test. The starting voltage of the drive test is 5.78V, and the initial brightness is maintained. The time above the brightness of 1600 Cd/m2 is .166

S 218 201224109 hours. &lt;Reference Example 2&gt; <Element of the electron transport layer towel to make the hearing compound (M)> The compound represented by the formula (1-10) is replaced with the compound represented by the formula (14), and Reference Example i was carried out in the same manner to obtain an organic rainbow. The ITO electrode was used as the anode. The fluorinated electrode was used as the cathode, and the strange current driving test was carried out by using the current density to obtain the initial value of 2 ed/m2. The driving test starting voltage was 7 75 V, and the time to maintain the brightness of 80% or more of the initial redundancy was 393 hours. &lt;Reference Example 3&gt; <Element for using compound (1_744) in the electron transport layer> Replacing the compound represented by the formula (M〇) with the compound of the formula (1-744) = otherwise For example, an organic material was obtained, and an ITO electrode was used as an anode, and a fluorination clock/sauer electrode was used as an anode 11 to obtain a current density of an initial luminance of 2 ed/m 2 to carry out an electrolysis driving test. The drive test voltage was 5 93 V, and the time to maintain the brightness of 80% or more of the initial redundancy was 213 hours. &lt;Comparative Example 1&gt; An organic device was obtained in the same manner as in Reference Example i except that the compound represented by the formula (1-10) was the compound (c). The lithium fluoride/aluminum electrode was used as the cathode by (10) and = as the anode, and was used to obtain :. Exemption of 2GGG ed/m2 electricity - real sister constant current drive test L drive test starting voltage is 4.78 v, maintaining the initial brightness above 8〇% of the time is 39 hours. 219 201224109 38673pif &lt;Comparative Example 2&gt; An organic &amp; element electrode was obtained as an anode, and a caged Langlu electrode was obtained in the same manner as in the reference example except that the compound represented by the formula (1-10) was replaced by the compound (9). As the cathode, a strange current driving test was carried out by using a current density of an initial luminance of 2000 cd/m2. The driving test starting voltage 4 4.74 v, (4) the time of brightness above 8〇% of the initial brightness is 24 hours. The above results are summarized in Table 6. [Table 6] · Electron transport layer——--(h) ~~ start voltage f\r\ Reference example 1 Compound (1-10) 166 5.78 Reference Example 2 Compound --- (1 4) 393 7.75 Reference Example 3 Comparative Example 1 You may 1 9 Compound (1-744) Compound (C) 213 tzzzziii^~--- 5.93 a no Chemical (D) Η*. /〇4.74

::: Example 4 to Reference Example 13 and Comparative Example 3, Comparative Example 参考 Reference Example 4 to Reference Example 13 and Comparative Example 3, Comparative Example 4 Γ分_枝定电流驱动检测的驱动Start=) Moxibustion: The time to hold the brightness of 8初始% or more of the initial brightness (1). The test case and its comparative examples are described in detail. Reference Example 4 to Reference Example 13 and Comparative Example (4) 3, Comparison The material composition of each layer of the light-emitting 7G piece t is as shown in Table 7 of τ.

S 220 201224109 38673pif [Table 7] Hole injection layer hole transport layer light-emitting layer electron transport layer host dopant reference example 4 HI NPD compound (E) compound (B) compound (1-10) Reference Example 5 HI NPD compound (E) Compound (B) Compound (1-5) Reference Example 6 HI NPD Compound (E) Compound (B) Compound (1-634) Reference Example 7 HI NPD Compound (E) Compound (B) Compound (1-744 Reference Example 8 HI NPD Compound (E) Compound (B) Compound (1-20) Reference Example 9 HI NPD Compound (E) Compound (B) Compound (1-24) Reference Example 10 HI NPD Compound (E) Compound ( B) Compound (1-743) Reference Example 11 HI NPD Compound (E) Compound (B) Compound (1-8710) Reference Example 12 HI NPD Compound (E) Compound (B) Compound (1-8711) Reference Example 13 HI NPD Compound (E) Compound (B) Compound (1-8712) Comparative Example 3 HI NPD Compound (E) Compound (B) Compound (F) Comparative Example 4 HI NPD Compound (E) Compound (B) Compound (6)

In Table 7, "HI" is N4, N4'-diphenyl-N4, N4'-bis(9-phenyl-9H-carbazol-3-yl)-[1, fluorene-biphenyl]-4 , 4'-diamine, compound (E) is 9-phenyl-10-(4-phenylnaphthalen-1-yl)anthracene, and compound (F) is 9,10-di([2,2,-linked) Pyridine]-5-yl)anthracene, the compound (G) is 2,7-bis([2,4'-bipyridyl]-6-yl)-9-phenyl-9-indazole. The chemical structure is expressed as follows with "Liq". [化158] 221 !; 201224109, ΆΛ.

&lt;Reference Example 4&gt;

&lt;Use of a component of a compound (Μ〇) in an electron transport layer&gt; A ITO of a thickness of 180 nm formed by a '贱 chain is ground to 15' = and a 26 mm x 28 face x 〇. 7 mm transmitted A glass substrate (manufactured by 〇pt) is used as a transparent supporting substrate. The transparent branch is ash-based; . The inspection device (manufactured by Vacuum Machine Guard Co., Ltd.) Ge ^ holds the β, and installs the molybdenum vapor deposition boat with the m, the indium-plated plate with the NPD, and the boat with the key. And a person who has a compound (8)...#_ molybdenum vapor deposition boat, and

S 222 201224109 38673pif A boat made of molybdenum for vapor deposition of a compound represented by the formula (MO), a boat for vapor deposition of molybdenum with Liq, a molybdenum boat filled with magnesium, and a tungsten filled with silver A boat for vapor deposition. &lt; The following layers were sequentially formed on the ITO film of the transparent supporting substrate. The vacuum chamber was decompressed to 5xlG_4Pa, and the boat was heated to a level of 40 meters to form a hole injection layer. Next, the boat was deposited with NAD. Heating, evaporation to a film thickness of 3 〇 nm and forming a hole transport layer. Next, the vapor deposition plate containing the compound (E) and the vapor deposition boat containing the compound (B) were simultaneously added and vapor-deposited to a film thickness of 35 nm to form a light-emitting layer. The steaming rate was adjusted in such a manner that the weight ratio of the compound to the compound (B) became about 95 to 5. Next, the steaming vessel loaded with the compound represented by the formula (1-1〇) was heated and vapor-deposited to a thickness of 15 nm to form an electron transporting layer. The vapor deposition rate of each layer was 0.01 nm/sec to 1 nm/sec. Thereafter, the steamed boat filled with Liq was heated and vapor-deposited to a film thickness of 1 nm at a vapor deposition rate of 〇1 鲁1 nm/sec to 0.1 nm/sec. Next, the boat loaded with magnesium and the boat loaded with silver were simultaneously heated and vapor-deposited to a thickness of 100 nm to form a cathode. In this case, the vapor deposition rate was adjusted so that the ratio of the atomic ratio of the town to the silver was 10 to 1, and the cathode was formed so that the vapor deposition rate was 0.1 nm to 1 nm, thereby obtaining an organic electroluminescence device. The ITO electrode was used as an anode and the magnesium/silver electrode was used as a cathode. When a f-flow voltage was applied, blue light emission having a wavelength of about 460 nm was obtained. Moreover, by performing a strange current drive test with a current density of 2000 cd/m2 to obtain an initial luminance, the driving test starting voltage is 5·09 V, and the initial 223 201224109 38673 pif brightness is maintained at 80% (brain ed/m2). The time of the above brightness is 245 &lt;Reference Example 5&gt;&lt;Elements of the compound (丨_5) used in the electron transport layer>

The compound (M0) was replaced with the compound (1_5), this: excipient The organic anal element was obtained by the method based on Reference Example 4. The ^ electrode is used as the anode 'counter / silver electrode as the impurity, # from the heart to obtain the initial ^2_ed / m2 ^ money density and the actual current axis test dynamic test starting voltage is 4_13 V, maintaining the initial brightness above the ancient The time is 246 hours. &lt;Reference Example 6 &lt;&lt;Use of element (1634) in the electron transport layer&gt;#Compound compound (M0) is replaced with compound (1·634), except by reference example 4 The organic EL element was obtained by a standard method. The electrode was used as an anode, and the ship/silver electrode was used as a button. The current-carrying test was carried out by using a current density of 2000 cd/m2 to obtain an initial luminance. drive

The starting voltage of the dynamic test was 5.41 V, and the time for maintaining the brightness of the initial brightness was 400 hours. &lt;Reference Example 7&gt;&lt;Component for using compound (1_744) in the electron transport layer&gt; Compound (M0) was replaced with compound (1744), and otherwise obtained by the method based on Reference Example 4 Organic el component. A constant current driving test was carried out by using a butadiene electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. drive

S 224 201224109 The starting voltage of the dynamic test is 4.96 V, and the time to maintain the brightness of 80% or more of the initial brightness is 231 hours. <Reference Example 8 &lt;&lt;Use of Element (1_2〇) in Electron Transport Layer&gt; Compound (1-10) was replaced with Compound (1-20), except by Reference Example 4 The organic EL element was obtained by a standard method. A constant current drive test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. The driving test starting voltage was 3.54 V, and the time to maintain the brightness of 80% or more of the initial brightness was 132 hours. ^ &lt;Reference Example 9&gt; <Elements using Compound (1-24) in the electron transport layer> Compound (1-10) was replaced with Compound (1-24), and reference was made to Reference Example 4 The organic EL element was obtained by the method. The IT/electrode was used as the anode and the money/silver electrode was used as the cathode, and a constant current drive test was carried out by using a current density of 2000 cd/m2 to obtain an initial degree of exemption. The driving test starting voltage was 5.26 V, and the time to maintain the brightness of 80% or more of the initial brightness was 265 hours. ~ &lt;Reference Example 10&gt;&lt;Use of element (1_743) in the electron transport layer&gt; Compound (1-10) was replaced with the compound (1-743), and the reference example 4 was used. An organic EL element was obtained by a standard method. A constant current driving test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 Cd/m2. Drive 225 201224109 38673pif The starting voltage of the dynamic test is 4.61 V, and the time to maintain the brightness of 80% or more of the initial brightness is 315 hours. &lt;Reference Example 11&gt;&lt;Component using compound (UMO) in electron transport layer&gt; Compound (1-10) was replaced with compound (1-8710), and reference was made to Reference Example 4 The organic EL element was obtained by the method. A constant current driving test was carried out by using an IT0 electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 Cd/m2. The drive test start voltage was 4.83 V, and the bright climb time to maintain the initial brightness of 80% or more was 430 hours. ~ &lt;Reference Example 12&gt;&lt;Component for using compound (1_8711) in the electron transport layer&gt; Compound (M0) was replaced with compound (i_8711), and the method based on Reference Example 4 was used. An organic EL element was obtained. A constant current driving test was carried out by using an IT crucible electrode as an anode and a town/silver electrode as a cathode by using a current density of an initial luminance of 2000 cd/m2. The driving test starting voltage was 185 V, and the time for maintaining the brightness of more than 8 % of the initial brightness was 229 hours. ~ &lt;Reference Example 13&gt; <Elements in which a compound (1-8712) is used in an electron transport layer> The compound (1-10) is replaced with a compound (^87^), and the reference example 4 is An organic EL element was obtained by a standard method. A constant current drive test was carried out by using a ruthenium electrode as an anode and a magnesium/silver electrode as a cathode by using a current density of an initial degree of protection of 2000 Cd/m2. drive

S 226 201224109 38673pif The starting voltage of the dynamic test is 4.00 V, and the time to maintain the brightness of 8初始% or more of the initial brightness is 240 hours. ^ &lt;Comparative Example 3&gt; An organic EL device was obtained by the method of Reference Example 4 except that the compound (1_1〇) was replaced with the compound (F). A constant current drive test was carried out by using a tantalum electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 cd/m2. The result is that the test start voltage is 3.86 V, and the time to maintain the brightness above 8〇% of the initial brightness is 196 hours. &lt;Comparative Example 4&gt; An organic EL device was obtained by the method of Reference Example 4 except that the compound (1-10) was replaced with the compound (G). A constant current drive test was carried out by using an IT crucible electrode as an anode and a magnesium/silver electrode as a cathode to obtain a current density of an initial luminance of 2000 Cd/m2. The result was 'drive test starting voltage 3.87 V, and the time to maintain the brightness above the initial brightness was 120 hours. The above results are summarized in Table 8. 227 201224109 38673pif [Table 8] The electron transfer layer maintains brightness of more than 80% of the initial brightness

[Industrial Applicability] According to a preferred aspect of the present invention, it is possible to provide an organic electroluminescence device which can improve the lifetime of a light-emitting element and is excellent in balance with a driving voltage, and has the organic electric excitation. A display device for an optical element, an illumination device having the organic electroluminescence element, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an organic electroluminescence device of the present embodiment 228 201224109 38673pif. [Description of Main Element Symbols] 100: Organic Electroluminescence Element 101: Substrate 102: Anode 103: Hole Injection Layer 104: Hole Transport Layer 105: Light Emitting Layer 106: Electron Transport Layer 107: Electron Injection Layer 108: Cathode

C 229

Claims (1)

201224109 VII. Scope of application for patents·· 1. A benzo[〇]° carbene compound, [Chemical 1] (A-4) In the above formula (1), R is an aryl group having a carbon number of 6 to 24 or a carbon number of A and A, and any one of them is selected from the above formula (a to aryl group of a to 24' of the above formula (A- 2) The base represented by the formula, the base represented by the above formula (a, 1), and the base represented by the formula represented by the above formula (A·4), and the base of the group represented by the group of the formula (A, 4) Base, one, one, another The ring contained in the junction of R, A and Α' may be substituted by a carbon group, a cyclohexyl group or a phenyl group, and constitutes a benzoxazole skeleton of the compound represented by the formula (1), and is substituted for R, Any hydrogen in A and A, may also be replaced by deuterium. 2. The benzo[c]carbazole compound according to the first aspect of the invention, wherein R is a group selected from the group consisting of the groups represented by the following formulas (r_1) to (R-20), S 230 201224109 38673pif Any one of A and A' is selected from the group represented by the following formula (Aii) to formula (A-1-3), and the following formula (A_2-1) to formula (A-2-18) The base represented by the formula (A-3-1) to the formula (A-3-6), and the following formula (A-4-1) to (A-4-6) One of the groups formed by the indicated groups, and the other is a group selected from the group consisting of the groups represented by the following formulas (A-5-1) to (A-5-11), and constitutes The benzoxazole skeleton of the compound represented by the formula (1), and any hydrogen of R, A and A' substituted there may be substituted by hydrazine, [Chemical 2] (R-1) (R-2) (R-10) (R-15) (R-16) (R-17) (R.18) (R-19) (R-20) 231 201224109. jow t -&gt;plf [Chemical 3] ^ ^ ^ (A-1-1) (A-1-2) (A-1-3) (A-2-1) ( A-2-2) (A-2-3) (A-2-4) (A-2-5) (A-2-7) (A-2-8) (A-2-9) (A -2-10) (A-2-11) (A-2-12) fO- Oo o (A-2-15) (A-2-16) (A-2-17) (A-2-18 ) (A-2-6) (A-2-13) (A-2-14) s~ (A-3-1) (A-3-2) (A-3-3) (A-3-4) (A-3-5) (A-3-6) (A-4-1) (A-4-2) (A-4-3) (A^-4) (A-4-5) (A-4-6) (A-5-1) (A-5-2) (A-5-3) (A-5-4) (A-5-5) (A-5-6) 8- ^ (A-5- 7) (A-5-8) (A-5-9) (A-5-10) (A-5-11) 〇 3. The benzo[c]carbazole as described in claim 1 a compound, wherein, S 232 201224109 380/jpif R is a group selected from the group consisting of the above formula (H), and the base represented by the formula (R-14) Any one of A and A' is selected from the group represented by the above formula (A-Μ)~式(a-^), ( 户·1)~式(A·2]1), A-3-1) a group represented by the formula (α_3·6) and a group of the groups represented by the formula (4)]) and the formula (4·6), and the other selected from the above One of the groups represented by the formula (A·2 3 4·1) and the group represented by the above formula (Α-5-8) to (A-5-11). 4. The benzo[c]-salt saliva compound according to claim 1, wherein R is a group selected from the group consisting of the above formula (1), and the group represented by the formula (R-11) Any one of A and A' is a group selected from the group represented by the above formula (Α·Μ) to (eight small 3), the group represented by the above formula (A_2]) to the formula (Α_2_18), and the above formula (Α- 3-1) one of the group represented by the formula (Α_3_6) and the group represented by the above formula (m) to formula (A-4-3), and the other is selected from the above formula (Α. 5·1) One of the groups represented by the group represented by the above formula (Α_5·8) to the formula (Α-5-10). a base represented by the formula 233 1 , a formula represented by the above formula (Α·2_υ~) (A_2_4), and a benzoxazole compound according to the first aspect of the invention, wherein 3 R is the above A group represented by the formula (R-1), the formula (R_1G) or the formula (R11), and any one of 4 A and A' is selected from the above formula (A_M) to the formula 201224109 (A-2-7) a group represented by the formula (Α·2_9), a group represented by the above formula (a_2_12), a group represented by the above formula (α·2]5), and the above formula (Α·叫~式 U-3-6) The group represented by the above formula (α·^) to the formula (α_4(1), which is represented by the group of the base group, and the other one is selected from the group represented by the above formula (A-5-1), a group represented by the above formula (A_5_8) and a group consisting of the groups represented by the above formula (A-5-9). 6. Benzo[c]pyrene as described in claim 1 And an azole compound, wherein R is a group represented by the above formula (R-〇 or formula (R-11), and any of A and A is selected from the group consisting of the above formula (A-1-1) to formula (a_i_3) The basis, the base represented by the above formula (Α_2_ι), and the above formula (A]·〗 a group represented by the above formula (Α·2_7) to (A-2-9), a group represented by the above formula (Α-2-12), and a group represented by the above formula (Α_3 6) And the group of the group represented by the above formula (Α_4_υ~) (Α_4_3), and the other is selected from the group represented by the above formula (AH) and represented by the above formula (Α-5-8) And a group of the group represented by the above formula (Α·5_9). 7. The benzo[Z]carbazole compound according to claim 1, which has the following formula (丨-335) ) said: [Chemical 4] S 234 201224109 JOU / jpif 8 · The benzo[c]carbazole compound of the first aspect of the patent application, which has the following formula (i-mo), formula (ι-m), formula (ι·43ι), Formula (1-383), Formula (1-384), Formula (1-376), Formula (1-360), Formula (1-408), Formula (1-237), Formula (1-189), Formula (1-455) or (I-59): [Chemical 5] 235 £ pif 201224109 9. An electron transporting material comprising a compound according to any one of clauses 1 to 8 of the above-mentioned patent application. 10. An organic electroluminescence device comprising: a counter electrode composed of an anode and a cathode; a light-emitting layer disposed between the counter electrode; disposed between the cathode and the light-emitting layer, and containing The electron transport layer and/or the electron injection layer of the electron transporting material described in S 236 201224109 \J\JI. The organic electroluminescent device according to claim 10, wherein at least one of the electron transport layer and the electron injecting layer further contains a hydroxyquinoline-based metal complex, a pyridine derivative, and a At least one of the group consisting of a thief derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative. The organic electroluminescent device of claim 11, wherein at least one of the electron transport layer and the electron injecting layer further comprises an oxidation selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, and alkali metals. a substance, an alkali metal halide, an alkaline earth metal oxide, an alkaline earth metal oxide, a rare earth metal oxide, a rare earth metal halide, an alkali metal organic complex, an organic compound of a soil test metal, and a rare earth At least one of the group consisting of organic complexes of metals. A display device having the organic electroluminescent device according to any one of claims 10 to 12. An organic electroluminescent device according to any one of the preceding claims. S 237