JP5007988B2 - Polycyclic fused-ring compounds, production methods thereof, and organic electroluminescent devices using the polycyclic fused-ring compounds - Google Patents

Description

  The present invention relates to a novel polycyclic fused ring compound, a production method thereof, an organic electroluminescent device using the novel polycyclic fused ring compound, and the like.

  Conventionally, display devices using light-emitting elements that emit electroluminescence have been studied variously because they can be reduced in power and thinned. Furthermore, organic electric field elements made of organic materials can be easily reduced in weight and size. Has been actively studied since. In particular, the development of organic materials with light emission characteristics such as blue, which is one of the three primary colors of light, and organic materials that have charge transporting ability (such as semiconductors and superconductors) such as holes and electrons The development of materials has been actively studied so far, regardless of whether it is a high molecular compound or a low molecular compound. For example, an organic electroluminescence device using a distyrylbenzene derivative having a stilbene skeleton as a light emitting layer has been reported (Japanese Patent Laid-Open No. 1-245078 (Patent Document 1), Appl. Phys. Lett., 56, 799, 1990 (Non-Patent Document 1)). However, since these distyrylbenzene derivatives are easily crystallized, the stability of the thin film is low, and the pi-conjugation is relatively small. Therefore, the light emitting efficiency of the organic EL device using them is low, which is not practical.

  As a material design capable of exhibiting high luminous efficiency and high charge transporting ability, there is a construction of a molecule having a pi-conjugated skeleton with high planarity. As one example, trans-stilbene derivatives cross-linked with silicon (WO 2004-18488 (Patent Document 2)) and trans-cross-links cross-linked with silicon and carbon as examples of trans-stilbene derivatives effectively extending pi-conjugation A stilbene derivative (Japanese Patent Laid-Open No. 2005-154410 (Patent Document 3)) has been reported. However, since these are synthesized using a metal reducing agent, substrates and substituents used in the reaction are limited. Silole derivatives have been reported as examples of trans-stilbene derivatives crosslinked with silicon and sulfur (WO2000-2886 (Patent Document 4), Organometallics, 23, 5622, 2004 (Non-patent Document 2)). These are synthesized by reacting a dilithiated product and a silane derivative, and the yield is low and the compounds that can be synthesized are limited.

JP-A-1-245078 WO2004-18488 JP 2005-154410 A WO2000-2886 Appl. Phys. Lett. , 56, 799, 1990 Organometallics, 23, 5622, 2004

  There is still a limited number of organic materials that have truly superior properties in terms of color purity, luminous efficiency, or carrier mobility and carrier injection, and the development of new pi-conjugated materials that meet these properties is desired. . The present invention has been made in view of these problems, and a purpose thereof is a novel polycyclic fusedring compound capable of exhibiting excellent properties as a light emitting material or a charge transporting material used in an organic EL device, and production thereof. It is an object to provide a method and an organic EL device using a novel polycyclic fused ring compound.

  As a result of intensive studies to solve the above problems, the present inventors have succeeded in producing a polycyclic fused ring compound having a skeleton represented by the following general formula (1). In addition, since this polycyclic fused ring compound exhibits high emission characteristics and charge transporting ability, a layer containing this polycyclic fused ring compound as a material for an organic electroluminescent element is disposed between a pair of electrodes to form an organic electroluminescent element. As a result, it was found that an organic electroluminescent device excellent in luminous efficiency, current efficiency, and the like can be obtained, and the present invention was completed.

  That is, the present invention provides the following polycyclic fused ring compound, a method for producing the polycyclic fused ring compound, an organic electroluminescent element material containing the polycyclic fused ring compound, and the organic electroluminescent element material. Provided is an organic electroluminescent device using a containing layer.

[1] A polycyclic fused ring compound having a skeleton represented by the following general formula (1).
(In the formula (1),
A ¹ and A ² are sulfur, SO ₂ , silicon or carbon, but ^one of A ¹ and A ² is sulfur or SO ₂ , and the other of A ¹ and A ² is silicon or carbon,
Ring structures B, C and D are each independently a 5-membered ring or a 6-membered ring,
p is a value of 0 or 1, but p is 1 when A ¹ or A ² is carbon. )

[2] The polycyclic fusedring compound according to the above [1], wherein the ring structures B, C and D are each independently a benzene ring, a thiophene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring or a pyridazine ring.

[3] The polycyclic fused ring compound described in the above [1] represented by the following general formula (2).
(In the formula (2) or (2A),
Each R ¹ is independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkylthio; , Optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted arylalkyl, optionally substituted arylalkoxy, optionally substituted Arylalkylthio, optionally substituted arylalkenyl, optionally substituted arylalkynyl, optionally substituted boryl, optionally substituted amino, optionally substituted silyl, optionally substituted Good silyloxy, optionally substituted arylsulfonyloxy, substituted Optionally substituted sulfonyloxy, optionally substituted aralkyl, optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl, adjacent groups bonded to each other To form a condensed ring,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, substituted Alkylthio, which may be substituted, aryl which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, arylalkyl which may be substituted, arylalkoxy which may be substituted, substituted Arylalkylthio which may be substituted, arylalkenyl which may be substituted, arylalkynyl which may be substituted, amino which may be substituted, silyl which may be substituted, silyloxy which may be substituted, substituted Arylsulfonyloxy which may be substituted, alkyl which may be substituted Sulfonyloxy, aralkyl optionally substituted, optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
n is independently 0, 1, 2, 3 or 4,
A ¹ and A ² are sulfur, SO ₂ or a group represented by the formula (2A), but ^one of A ¹ and A ² is sulfur or SO ₂ , and the other of A ¹ and A ^{2 is} the other It is group represented by Formula (2A). )

[4] Each R ¹ is independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkoxy having 1 to 20 carbon atoms, or substituted having 5 to 30 carbon atoms. Optionally substituted aryl, optionally substituted aromatic boryl, optionally substituted aromatic amino, optionally substituted silyl, optionally substituted heteroaryl or halogen,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted aryl having 5 to 30 carbon atoms, or optionally substituted heteroaryl. Is,
The condensed polycyclic compound described in [3] above.

[5] R ¹ is independently hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, phenyl, naphthyl, diarylboryl, dialkylamino, Diarylamino, trialkylsilyl, thienyl, pyridyl, F, Cl, Br or I;
R ³ and R ⁴ are each independently methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl, naphthyl, thienyl or pyridyl.
The condensed polycyclic compound described in [3] above.

[6] The polycyclic fused ring compound described in the above [3] represented by the following formula (2-1) or (2-2).

[7] The polycyclic fused ring compound according to the above [1], which has a skeleton represented by the following formula (2-3), (2-4), (2-5) or (2-6).
(However, in each formula, A ¹ is silicon, and “S (O) 2” is independently “S” or “SO ₂ ”.)

[8] The polycyclic fused ring compound described in the above [1] represented by the following general formula (3).
(In Formula (3) or (3A),
R ¹ and R ² are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, substituted Alkylthio, which may be substituted, aryl which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, arylalkyl which may be substituted, arylalkoxy which may be substituted, substituted Optionally substituted arylalkylthio, optionally substituted arylalkenyl, optionally substituted arylalkynyl, optionally substituted boryl, optionally substituted amino, optionally substituted silyl, substituted Optionally substituted silyloxy, optionally substituted arylsulfonyloxy An optionally substituted alkylsulfonyloxy, an optionally substituted aralkyl, an optionally substituted heteroaryl, an optionally substituted cycloalkyl, a halogen, cyano, nitro or hydroxyl, and adjacent groups are They may combine with each other to form a condensed ring,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, substituted Alkylthio, which may be substituted, aryl which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, arylalkyl which may be substituted, arylalkoxy which may be substituted, substituted Arylalkylthio which may be substituted, arylalkenyl which may be substituted, arylalkynyl which may be substituted, amino which may be substituted, silyl which may be substituted, silyloxy which may be substituted, substituted Arylsulfonyloxy which may be substituted, alkyl which may be substituted Sulfonyloxy, aralkyl optionally substituted, optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
m is 0, 1 or 2, n is each independently 0, 1, 2, 3 or 4,
A ¹ and A ² are sulfur, SO ₂ or a group represented by the formula (3A), but ^one of A ¹ and A ² is sulfur or SO ₂ , and the other of A ¹ and A ^{2 is} the other It is group represented by Formula (3A). )

[9] R ¹ and R ² are each independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkoxy having 1 to 20 carbon atoms, or 5 to 30 carbon atoms. An optionally substituted aryl, an optionally substituted aromatic boryl, an optionally substituted aromatic amino, an optionally substituted silyl, an optionally substituted heteroaryl or halogen,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted aryl having 5 to 30 carbon atoms, or optionally substituted heteroaryl. Is,
The polycyclic fusedring compound described in [8] above.

[10] R ¹ and R ² are each independently hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, phenyl, naphthyl, diarylboryl, Dialkylamino, diarylamino, trialkylsilyl, thienyl, pyridyl, F, Cl, Br or I;
R ³ and R ⁴ are each independently methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl, naphthyl, thienyl or pyridyl.
The polycyclic fusedring compound described in [8] above.

[11] The polycyclic fused ring compound described in the above [8] represented by the following formula (3-1) or (3-2).

[12] The polycyclic fused ring compound according to the above [1], which has a skeleton represented by the following formula (3-3), (3-4), (3-5) or (3-6).
(However, in each formula, A ¹ and A ² are silicon, and “S (O) 2” is independently “S” or “SO ₂ ”.)

[13] The polycyclic fused ring compound described in the above [1] represented by the following general formula (4).
(In the formula (4) or (4A),
R ¹ and R ² are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, substituted Alkylthio, which may be substituted, aryl which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, arylalkyl which may be substituted, arylalkoxy which may be substituted, substituted Optionally substituted arylalkylthio, optionally substituted arylalkenyl, optionally substituted arylalkynyl, optionally substituted boryl, optionally substituted amino, optionally substituted silyl, substituted Optionally substituted silyloxy, optionally substituted arylsulfonyloxy An optionally substituted alkylsulfonyloxy, an optionally substituted aralkyl, an optionally substituted heteroaryl, an optionally substituted cycloalkyl, a halogen, cyano, nitro or hydroxyl, and adjacent groups are They may combine with each other to form a condensed ring,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, substituted May be an aralkyl, an optionally substituted heteroaryl, an optionally substituted cycloalkyl, cyano, nitro or hydroxyl;
m is 0, 1 or 2, n is each independently 0, 1, 2, 3 or 4,
A ¹ and A ² are groups represented by sulfur, SO ₂ or formula (4A), but ^one of A ¹ and A ² is sulfur or SO ₂ , and the other of A ¹ and A ^{2 is} the other It is group represented by Formula (4A). )

[14] R ¹ and R ² are each independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkoxy having 1 to 20 carbon atoms, or 5 to 30 carbon atoms. An optionally substituted aryl, an optionally substituted aromatic boryl, an optionally substituted aromatic amino, an optionally substituted silyl, an optionally substituted heteroaryl or halogen,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted aryl having 5 to 30 carbon atoms, or substituted having 2 to 30 carbon atoms. Is optionally heteroaryl,
The polycyclic fusedring compound described in [13] above.

[15] R ¹ and R ² are each independently hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, phenyl, naphthyl, diarylboryl, Dialkylamino, diarylamino, trialkylsilyl, thienyl, pyridyl, F, Cl, Br or I;
R ³ and R ⁴ are each independently hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl, naphthyl, thienyl, pyridyl,
The polycyclic fusedring compound described in [13] above.

[16] The polycyclic fused ring compound described in the above [13] represented by the following formula (4-1) or (4-2).
(In the formula, “Ph” is a phenyl group.)

[17] An n-merized polycyclic fused ring compound obtained by n-merization of the polycyclic fused ring compound described in the above [1] to [16]. However, n is 2-8.

[18] The n-merized polycyclic fused ring compound according to the above [17], wherein n is 2.

[19] A synthetic intermediate of a polycyclic fused ring compound represented by the following general formula (5) is reacted with an organometallic base to be metalated by halogen-metal exchange, and then the generated anion is captured by sulfur. A method for producing a polycyclic fused ring compound, wherein the polycyclic fused ring compound according to [3] is obtained.
(In Formula (5),
X is hydrogen, halogen, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryloxy, or optionally substituted arylthio, or optionally substituted silyl. Yes,
Y is Cl, Br or I;
Each R ¹ is independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, optionally substituted alkylthio; , Optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted arylalkyl, optionally substituted arylalkoxy, optionally substituted Arylalkylthio, optionally substituted arylalkenyl, optionally substituted arylalkynyl, optionally substituted boryl, optionally substituted amino, optionally substituted silyl, optionally substituted Good silyloxy, optionally substituted arylsulfonyloxy, substituted Optionally substituted sulfonyloxy, optionally substituted aralkyl, optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl, adjacent groups bonded to each other To form a condensed ring,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, substituted Alkylthio, which may be substituted, aryl which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, arylalkyl which may be substituted, arylalkoxy which may be substituted, substituted Arylalkylthio which may be substituted, arylalkenyl which may be substituted, arylalkynyl which may be substituted, amino which may be substituted, silyl which may be substituted, silyloxy which may be substituted, substituted Arylsulfonyloxy which may be substituted, alkyl which may be substituted Sulfonyloxy, aralkyl optionally substituted, optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
n is each independently 0, 1, 2, 3 or 4. )

[20] Each R ¹ is independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkoxy having 1 to 20 carbon atoms, or substituted having 5 to 30 carbon atoms. Optionally substituted aryl, optionally substituted aromatic boryl, optionally substituted aromatic amino, optionally substituted silyl, optionally substituted heteroaryl or halogen,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted aryl having 5 to 30 carbon atoms, or optionally substituted heteroaryl. Is,
The manufacturing method of the polycyclic fused-ring compound as described in said [19].

[21] R ¹ is each independently hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, phenyl, naphthyl, diarylboryl, dialkylamino, Diarylamino, trialkylsilyl, thienyl, pyridyl, F, Cl, Br or I;
R ³ and R ⁴ are each independently methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl, naphthyl, thienyl or pyridyl.
The manufacturing method of the polycyclic fused-ring compound as described in said [19].

[22] A synthetic intermediate of a polycyclic fused ring compound represented by the following general formula (6) or (7) is reacted with an organometallic base to be metalated by halogen-metal exchange, and then the generated anion is captured with sulfur. By doing this, the manufacturing method of the polycyclic fused ring compound which obtains the polycyclic fused ring compound as described in said [8].
(In the formulas (6) and (7),
X is hydrogen, halogen, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryloxy, or optionally substituted arylthio, or optionally substituted silyl. Yes,
Y is Cl, Br or I;
R ¹ and R ² are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, substituted Alkylthio, which may be substituted, aryl which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, arylalkyl which may be substituted, arylalkoxy which may be substituted, substituted Optionally substituted arylalkylthio, optionally substituted arylalkenyl, optionally substituted arylalkynyl, optionally substituted boryl, optionally substituted amino, optionally substituted silyl, substituted Optionally substituted silyloxy, optionally substituted arylsulfonyloxy An optionally substituted alkylsulfonyloxy, an optionally substituted aralkyl, an optionally substituted heteroaryl, an optionally substituted cycloalkyl, a halogen, cyano, nitro or hydroxyl, and adjacent groups are They may combine with each other to form a condensed ring,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, substituted Alkylthio, which may be substituted, aryl which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, arylalkyl which may be substituted, arylalkoxy which may be substituted, substituted Arylalkylthio which may be substituted, arylalkenyl which may be substituted, arylalkynyl which may be substituted, amino which may be substituted, silyl which may be substituted, silyloxy which may be substituted, substituted Arylsulfonyloxy which may be substituted, alkyl which may be substituted Sulfonyloxy, aralkyl optionally substituted, optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
m is 0, 1 or 2, and n is independently 0, 1, 2, 3 or 4. )

[23] R ¹ and R ² each independently represent hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted alkoxy having 1 to 20 carbon atoms, or 5 to 30 carbon atoms. An optionally substituted aryl, an optionally substituted aromatic boryl, an optionally substituted aromatic amino, an optionally substituted silyl, an optionally substituted heteroaryl or halogen,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl having 1 to 20 carbon atoms, optionally substituted aryl having 5 to 30 carbon atoms, or optionally substituted heteroaryl. Is,
The manufacturing method of the polycyclic fused-ring compound as described in said [22].

[24] R ¹ and R ² are each independently hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, phenyl, naphthyl, diarylboryl, Dialkylamino, diarylamino, trialkylsilyl, thienyl, pyridyl, F, Cl, Br or I;
R ³ and R ⁴ are each independently methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl, naphthyl, thienyl or pyridyl.
The manufacturing method of the polycyclic fused-ring compound as described in said [22].

[25] A material for an organic electroluminescence device comprising the polycyclic fused ring compound or the n-merized polycyclic fused ring compound according to any one of [1] to [18].

[26] having a pair of electrodes composed of an anode and a cathode, and one or a plurality of layers disposed between the pair of electrodes and containing the material for an organic electroluminescent element according to [25],
Organic electroluminescent device.

[27] The organic electroluminescent element according to the above [26], wherein the one or more layers containing the material for an organic electroluminescent element are a luminescent layer.

[28] A display device comprising the organic electroluminescent element as described in [26] or [27].

[29] A lighting device comprising the organic electroluminescent element as described in [26] or [27].

  According to a preferred embodiment of the present invention, for example, a polycyclic fused ring compound having excellent characteristics as a light emitting device material can be provided. Further, it is possible to provide an organic electroluminescent device having excellent characteristics in terms of color purity and luminous efficiency, or carrier mobility and carrier injection. In addition, it can be applied to many kinds of organic layers constituting organic electroluminescent devices by changing some condensed ring structures and substituents of the polycyclic fused ring compound which is the main skeleton. A material for an electroluminescent element can be provided.

1. Description of Compounds The polycyclic fused ring compound of the present invention will be described in detail.
The polycyclic fused ring compound according to the present invention is a compound having a skeleton represented by the general formula (1).

1-1. Compound having a skeleton represented by general formula (1) A ¹ and A ^{2 in} general formula (1) are sulfur, SO ₂ , silicon or carbon, and one of A ¹ and A ² is sulfur or SO 2. ₂ and the other of A ¹ and A ² is silicon or carbon. When A ¹ or A ² is silicon, it is preferable that the silicon has two bonding groups (a bonding group different from the two bonds forming a 5-membered ring). In the case where A ¹ or A ² is carbon, the carbon preferably has two linking groups (a linking group different from two bonds forming a 5-membered ring). In addition, about the coupling | bonding group to silicon and carbon, it demonstrates in the column of the detailed description of the polycyclic fused-ring compound represented by General formula (2), (3) or (4) mentioned below.

  Ring structures B, C and D are each independently a 5-membered or 6-membered ring, preferably selected from a benzene ring, thiophene ring, pyridine ring, pyrazine ring, pyrimidine ring or pyridazine ring. . More preferred are a benzene ring, a thiophene ring, and a pyridine ring.

  Preferable examples of the compound having a skeleton represented by the general formula (1) include a polycyclic fused ring compound represented by the above general formula (2), the above general formula (3), and the above general formula (4). Can be given.

The polycyclic fused-ring compound according to the present invention has a structure in which a trans-stilbene skeleton is cross-linked, and has high planarity and effectively expanded pi-conjugation. be able to. In the polycyclic fused ring compound according to the present invention, sulfur or SO ₂ introduced into the ring structure functions as an electron donating group or an electron withdrawing group, respectively. When sulfur is introduced into the ring structure to impart electron donating properties, it becomes a useful material, for example, as a hole transporting material, while when SO ₂ is introduced into the ring structure to impart electron withdrawing properties. For example, since it becomes a material useful as an electron transport material, the polycyclic fused-ring compound according to the present invention is a highly versatile compound as a material for an organic electroluminescence device.

1-2. Compound represented by formula (2) The compound represented by formula (2) will be described.

The “alkyl” of the “optionally substituted alkyl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) may be linear, branched or cyclic. Examples thereof include linear or branched alkyl having 1 to 20 carbon atoms or cyclic alkyl. Preferred “alkyl” is alkyl having 1 to 12 carbons. More preferable “alkyl” is alkyl having 1 to 6 carbon atoms. Particularly preferred “alkyl” is alkyl having 1 to 4 carbon atoms. Specific examples of “alkyl” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl and the like. .

The “alkenyl” of the “optionally substituted alkenyl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) may be linear or branched. There are 20 straight or branched alkenyls. Preferred “alkenyl” is alkenyl having 2 to 12 carbon atoms. More preferable “alkenyl” is alkenyl having 2 to 6 carbon atoms. Particularly preferred “alkenyl” is alkenyl having 2 to 4 carbon atoms. Specific examples include vinyl, propenyl, isopropenyl, allyl, butenyl, pentenyl, geranyl, farnesyl and the like.

The “alkynyl” of the “optionally substituted alkynyl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) may be linear or branched. There are 20 straight or branched alkynyls. Preferred “alkynyl” is alkynyl having 2 to 12 carbon atoms. More preferable “alkynyl” is alkynyl having 2 to 6 carbon atoms. Particularly preferred “alkynyl” is alkynyl having 2 to 4 carbon atoms. Specific examples include ethynyl, propynyl, butynyl and the like.

Examples of “alkoxy” of “optionally substituted alkoxy” in R ¹ , R ³ and R ⁴ of formula (2) or (2A) include alkoxy having 1 to 20 carbon atoms. Preferred “alkoxy” is alkoxy having 1 to 15 carbon atoms. More preferable “alkoxy” is alkoxy having 1 to 10 carbon atoms. Specific examples of “alkoxy” include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, cycloheptyloxy, octyl And oxy, cyclooctyloxy, phenoxy and the like.

Examples of “alkylthio” of “optionally substituted alkylthio” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include alkylthio having 1 to 20 carbon atoms. Preferred “alkylthio” is alkylthio having 1 to 15 carbon atoms. More preferable “alkylthio” is alkylthio having 1 to 10 carbon atoms. Specific examples of “alkylthio” include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, s-butylthio, t-butylthio, pentylthio, cyclopentylthio, hexylthio, cyclohexylthio, heptylthio, cycloheptylthio, octylthio, cyclo Examples include octylthio.

Examples of “aryl” of “optionally substituted aryl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include aryl having 5 to 30 carbon atoms. Preferred “aryl” is aryl having 5 to 25 carbon atoms. More preferable “aryl” is aryl having 5 to 20 carbon atoms. Specific examples of “aryl” include phenyl, tolyl, xylyl, biphenylyl, naphthyl, anthracenyl, phenanthryl, terphenylyl, fluorenyl, pyrenyl and the like. Particularly preferred “aryl” is phenyl or naphthyl.

“Aryloxy” of “optionally substituted aryloxy” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) includes aryloxy having 6 to 20 carbon atoms. Preferred “aryloxy” is aryloxy having 6 to 16 carbon atoms. More preferable “aryloxy” is aryloxy having 6 to 13 carbon atoms. Specific examples of “aryloxy” include phenyloxy, naphthyloxy, anthracenyloxy, phenanthryloxy and the like. The “aryl” in “aryloxy” includes the aryl described above.

“Arylthio” of “optionally substituted arylthio” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) includes arylthio having 6 to 30 carbon atoms. Preferred “arylthio” is arylthio having 6 to 25 carbon atoms. More preferable “arylthio” is arylthio having 6 to 20 carbon atoms. Specific “arylthio” includes phenylthio, naphthylthio, anthracenylthio, phenanthrylthio and the like. The “aryl” in “arylthio” includes the aryl described above.

Examples of “arylalkyl” of “optionally substituted arylalkyl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include arylalkyl having 6 to 30 carbon atoms. Preferred “arylalkyl” is arylalkyl having 6 to 25 carbon atoms. More preferred “arylalkyl” is arylalkyl having 6 to 20 carbon atoms. Specific “arylalkyl” includes arylmethyl, arylethyl and the like. The “aryl” in “arylalkyl” includes the above-mentioned aryl. The “alkyl” in “arylalkyl” includes the above-mentioned alkyl.

Examples of “arylalkoxy” of “optionally substituted arylalkoxy” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include arylalkoxy having 6 to 30 carbon atoms. Preferred “arylalkoxy” is arylalkoxy having 6 to 25 carbon atoms. More preferred “arylalkoxy” is arylalkoxy having 6 to 20 carbon atoms. Specific examples of “arylalkoxy” include arylmethoxy and arylethoxy. The “aryl” in “arylalkoxy” includes the aryl described above. In addition, “alkoxy” in “arylalkoxy” includes alkoxy as described above.

Examples of the “arylalkylthio” of the “optionally substituted arylalkylthio” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include arylalkylthio having 6 to 30 carbon atoms. Preferred “arylalkylthio” is arylalkylthio having 6 to 25 carbon atoms. More preferred “arylalkylthio” is arylalkylthio having 6 to 20 carbon atoms. Specific “arylalkylthio” includes arylmethoxy, arylethoxy and the like. The “aryl” in “arylalkylthio” includes the aryl described above. The “alkylthio” of “arylalkylthio” includes the alkylthio described above.

Examples of the “arylalkenyl” of the “optionally substituted arylalkenyl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include arylalkenyl having 6 to 30 carbon atoms. Preferred “arylalkenyl” is arylalkenyl having 6 to 25 carbon atoms. More preferable “arylalkenyl” is arylalkenyl having 6 to 20 carbon atoms. Specific examples of “arylalkenyl” include arylvinyl, arylpropenyl, arylisopropenyl and the like. The “aryl” in “arylalkenyl” includes the aryl described above. The “alkenyl” of “arylalkenyl” includes the above-mentioned alkenyl.

Examples of the “arylalkynyl” of the “optionally substituted arylalkynyl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include arylalkynyl having 6 to 30 carbon atoms. Preferred “arylalkynyl” is arylalkynyl having 6 to 25 carbon atoms. More preferable “arylalkynyl” is arylalkynyl having 6 to 20 carbon atoms. Specific examples of “arylalkynyl” include arylethynyl, arylpropynyl and the like. The “aryl” in “arylalkynyl” includes the aryl described above. Further, “alkynyl” of “arylalkynyl” includes alkynyl described above.

Specific examples of the “optionally substituted boryl” in R ¹ of the general formula (2) or (2A) include diarylboryl such as diphenylboryl, ditolylboryl, dimesityrylboryl, dianthrylboryl, anthrylmesitylboryl and the like. Etc. Examples of the “substituent” of substituted boryl include ortho-disubstituted phenyl. Specific “substituents” include xylyl, mesityl, diisopropylphenyl, triisopropylphenyl, terphenyl and the like.

Specific examples of the “optionally substituted amino” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include amino; methylamino, ethylamino, cyclohexylamino, acetylamino and the like Alkylalkyl; dialkylamino such as dimethylamino, diethylamino, and dibutylamino; and diarylamino such as diphenylamino.

Specific examples of the “optionally substituted silyl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include trimethylsilyl, t-butyldimethylsilyl, t-butyldiphenylsilyl, Examples include trialkylsilyl such as triphenylsilyl, and alkoxysilyl such as trimethoxysilyl, triethoxysilyl, and tributoxysilyl.

As “optionally substituted silyloxy” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A), trialkylsilyloxy (for example, trimethylsilyloxy, triethylsilyloxy, triisopropylsilyloxy, Diethylisopropylsilyloxy, dimethylisopropylsilyloxy, di-t-butylmethylsilyloxy, isopropyldimethylsilyloxy, t-butyldimethylsilyloxy, texyldimethylsilyloxy, etc.), trialkylarylsilyloxy (for example, And diphenylmethylsilyloxy, t-butyldiphenylsilyloxy, t-butyldimethoxyphenylsilyloxy, triphenylsilyloxy, etc.).

Examples of “optionally substituted arylsulfonyloxy” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include benzenesulfonyloxy, p-toluenesulfonyloxy, mesitylenesulfonyloxy, naphthalenesulfonyloxy Etc.

Examples of the “optionally substituted alkylsulfonyloxy” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) include methanesulfonyloxy, ethanesulfonyloxy, butanesulfonyloxy, octanessulfonyloxy, trifluoro Examples include lomethanesulfonyloxy.

The “aralkyl” of the “optionally substituted aralkyl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) includes an optionally substituted aralkyl having 7 to 20 carbon atoms. It is done. Preferred “aralkyl” is aralkyl having 7 to 15 carbon atoms. More preferable “aralkyl” is aralkyl having 7 to 10 carbon atoms. Specific examples of “aralkyl” include benzyl, phenylethyl, methylbenzyl (tolubenzyl), naphthylmethyl (mennaphthyl), and the like.

The “heteroaryl” of “optionally substituted heteroaryl” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A) is, for example, an oxygen atom or sulfur other than a carbon atom as a ring atom And heterocyclic groups containing 1 to 5 heteroatoms selected from atoms and nitrogen atoms. Focusing on carbon atoms that are constituent atoms other than heteroatoms, for example, heteroaryl having 2 to 30 carbon atoms, preferably heteroaryl having 2 to 25 carbon atoms, more preferably heteroaryl having 2 to 20 carbon atoms Is given. For example, furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [b ] Thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl Phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathinyl, Antoreniru, and the like indolizinyl, such as thienyl, oxadiazolyl, pyridyl, benzo [b] thienyl, quinolyl, such as carbazolyl are preferable.

Examples of “cycloalkyl” of “optionally substituted cycloalkyl” in R ¹ , R ³ and R ⁴ of formula (2) or (2A) include cycloalkyl having 3 to 10 carbon atoms. . Preferred “cycloalkyl” is cycloalkyl having 3 to 8 carbon atoms. More preferred “cycloalkyl” is cycloalkyl having 3 to 5 carbon atoms. Specific examples of “cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, and cyclooctyl.

Examples of the “halogen” in R ¹ , R ³ and R ⁴ in the general formula (2) or (2A) include F, Cl, Br, I and the like.

As the “substituent” in R ¹ , R ³ and R ⁴ of the general formula (2) or (2A), for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, Cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, cyclooctyl, alkyl such as trifluoromethyl; aryl such as phenyl, naphthyl, anthracenyl, phenanthryl; methylphenyl, ethylphenyl, s-butylphenyl, t-butylphenyl, Alkylaryl such as 1-methylnaphthyl, 2-methylnaphthyl, 4-methylnaphthyl, 1,6-dimethylnaphthyl, 4-t-butylnaphthyl; pyridyl, quinazolinyl, quinolyl, pyrimidinyl, furyl, thienyl, pyrrolyl, imidazolyl, te Heterocycles such as trazolyl and phenanthrolinyl; cyano and the like. The number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2.

  As n in General formula (2), 0-4 are mentioned, Preferably it is 0-2, More preferably, it is 0 or 1.

As a further specific example of the compound represented by the general formula (2), for example, a compound represented by the above formula (2-1) or (2-2) can be exemplified.
Examples of the ring structure include polycyclic fused ring compounds having a skeleton represented by the above formula (2-3), (2-4), (2-5) or (2-6), And polycyclic condensed ring compounds having a skeleton represented by the following formula (2-7) or (2-8). In each formula, A ¹ is silicon, A ³ is carbon, and “S (O) 2” is “S” or “SO ₂ ”.

1-3. Compound represented by formula (3) The compound represented by formula (3) will be described.
R ¹ , R ² , R ³ and R ^{4 in the} general formula (3) or (3A) are the same as those described in the description of R ¹ , R ³ and R ^{4 in} the general formula (2) or (2A). The same thing is preferable.

  Examples of m in the general formula (3) or (3A) include 0 to 2, preferably 0 to 1, and more preferably 0. Moreover, as n in General formula (3) or (3A), although 0-4 are mention | raise | lifted, Preferably it is 0-2, More preferably, it is 0 or 1.

As a further specific example of the compound represented by the general formula (3), for example, a compound represented by the general formula (3-1) or (3-2) can be given.
Examples of the ring structure include polycyclic fused ring compounds having a skeleton represented by the general formula (3-3), (3-4), (3-5) or (3-6), Can be a polycyclic fused ring compound having a skeleton represented by the following formula (3-7) or (3-8). In each formula, A ¹ is silicon, and “S (O) 2” is independently “S” or “SO ₂ ”.

1-4. The compound represented by the general formula (4) The compound represented by the general formula (4) will be described.
Examples of R ¹ and R ² in the general formula (4) or (4A) include the same as those described in the description of R ¹ , R ³ and R ^{4 in} the general formula (2) or (2A). Similar ones are preferred.
R ³ and R ⁴ in general formula (4) or (4A) are hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted. Examples thereof include aryl, optionally substituted aralkyl, optionally substituted heteroaryl, optionally substituted cycloalkyl, cyano, nitro, and hydroxyl. For each of these linking groups, the general formula (2 ) Or (2A) are the same as those described in the description of R ¹ , R ³ and R ⁴ , and the same are preferable.

  Examples of m in the general formula (4) or (4A) include 0 to 2, preferably 0 to 1, and more preferably 0. Moreover, as n in General formula (4) or (4A), although 0-4 are mention | raise | lifted, Preferably it is 0-2, More preferably, it is 0 or 1.

As a further specific example of the compound represented by the general formula (4), for example, a compound represented by the general formula (4-1) or (4-2) can be exemplified.
Examples of the ring structure modification include polycyclic condensed ring compounds having a skeleton represented by the following formula (4-3), (4-4), (4-5) or (4-6). Can do. In each formula, A ¹ and A ² are carbon, and “S (O) 2” is independently “S” or “SO ₂ ”.

1-5. n-merized polycyclic fused ring compound The above-mentioned polycyclic fused ring compound may be n-merized to constitute an n-merized polycyclic fused ring compound. Here, n is 2 to 8, preferably 2 to 4, and more preferably 2.
This n-merized polycyclic fused ring compound is represented by the following general formula (8) when described using the above general formula (1).

In formula (8),
L represents a simple bond or an n-valent linking group, and may be aliphatic or aromatic. In the case of aliphatic, L may be a chain or a ring. Examples of L include carbon, nitrogen, benzene, naphthalene, phenalene, phenanthrene, anthracene, triphenylene, pyrene, naphthacene, perylene, pentacene, tetraphenylene, thiophene, thiopyran, thiochromene, pyridine, pyrazine, pyrimidine, pyridazine, quinolidine, or isoquinoline. Etc.
In addition, about which part of the polycyclic fused ring compound L binds, not only ring B but also a 5-membered ring having A ¹ , a 5-membered ring having A ² or ring C may be used.

Preferred examples of the n-merized polycyclic fused ring compound include those shown below.

2. Production Method of Polycyclic Fused Ring Compound The polycyclic fused ring compounds represented by the following formulas (2-9), (3-9) and (3-10) according to the present invention are as shown in the following reaction formula. By reacting synthetic intermediates represented by the following formulas (5), (6) and (7) respectively with an organometallic base and metalating by halogen-metal exchange, the generated anions are captured with sulfur. Can be synthesized.

  In the above formulas (5), (6) and (7), X is hydrogen, halogen, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryloxy, substituted. Arylthio which may be substituted, silyl which may be substituted are mentioned, and hydrogen or alkoxy is particularly useful. Examples of Y include Cl, Br and I, and Br and I are particularly useful.

  In this case, as the organometallic base to be used, organolithium reagents such as n-BuLi, s-BuLi and t-BuLi, organomagnesium reagents such as alkyl Grignard reagents and alkylmagnesium amides, or alkylzinc reagents can be used. The solvent used in the reaction is not particularly limited as long as it is inert to these organometallic bases, and ether solvents such as THF, diethyl ether and 1,2-dimethoxyethane, aromatic solvents such as benzene and toluene, An aliphatic solvent such as pentane or hexane can be used.

  The reaction is preferably performed in an inert gas, and nitrogen, argon, or the like can be used as the inert gas. The reaction temperature can be −100 ° C. to + 100 ° C., preferably −78 ° C. to + 30 ° C. There is no restriction | limiting in particular in reaction time, What is necessary is just to stop reaction when reaction has fully progressed. The reaction may be traced by a general analytical means such as NMR or chromatography, and the end point of the reaction may be determined at an optimal time.

  Polycyclic fused ring compounds represented by the following formulas (4-7) and (4-8) are described in known literature (for example, J. Am. Chem. Soc., 126, 6987, 2004). It can be synthesized by the method and the method described in the examples of the present specification.

  Polycyclic fused ring compounds represented by the following formulas (2-9 ′), (3-9 ′), (3-10 ′), (4-7 ′) and (4-8 ′) are known. (For example, Tetrahedron Letters, 31, 5955, 1990) or a method described in the examples of the present specification.

3. Organic electroluminescent device The organic electroluminescent device according to the present invention is a polycyclic fused ring having a pair of electrodes composed of an anode and a cathode and a skeleton represented by the general formula (1), which is disposed between the pair of electrodes. An organic electroluminescence device having one or more layers containing a compound as a material for an organic electroluminescence device.
The organic electroluminescent element according to this embodiment will be described in detail based on the drawings. FIG. 1 is a schematic cross-sectional view showing an organic electroluminescent element according to this embodiment.

<Structure of organic electroluminescence device>
An organic electroluminescent device 100 shown in FIG. 1 includes a substrate 101, an anode 102 provided on the substrate 101, a hole injection layer 103 provided on the anode 102, and a hole injection layer 103. A hole transport layer 104 provided on the light emitting layer 105, a light emitting layer 105 provided on the hole transport layer 104, an electron transport layer 106 provided on the light emitting layer 105, and an electron transport layer 106. And the cathode 108 provided on the electron injection layer 107.

  The organic electroluminescent element 100 is manufactured in the reverse order, for example, the substrate 101, the cathode 108 provided on the substrate 101, the electron injection layer 107 provided on the cathode 108, and the electron injection layer. An electron transport layer 106 provided on 107, a light-emitting layer 105 provided on the electron transport layer 106, a hole transport layer 104 provided on the light-emitting layer 105, and a hole transport layer 104 A structure including the hole injection layer 103 provided above and the anode 102 provided on the hole injection layer 103 may be employed.

  Not all of the above layers are necessary, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection are included. The layer 107 is an arbitrarily provided layer. Moreover, each said layer may consist of a single layer, respectively, and may consist of multiple layers.

  As an aspect of the layer constituting the organic electroluminescence device, in addition to the above-described configuration aspect of “substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode”, "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 / light emitting layer / “Electron transport layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron injection layer / cathode”, “substrate / anode / hole injection layer / light emitting layer / electron transport” Layer / cathode ”,“ substrate / anode / hole injection layer / hole transport layer / light emitting layer / cathode ”,“ substrate / anode / hole injection layer / light emitting layer / cathode ”,“ substrate / anode / hole transport ” Layer / light emitting layer / cathode ”,“ substrate / anode / light emitting layer / electron transport layer / cathode ”,“ substrate / anode / light emitting layer / electron injection layer / cathode ”,“ substrate / anode / light emitting layer / cathode ” An aspect may be sufficient.

<Substrate in organic electroluminescence device>
The substrate 101 serves as a support for the organic electroluminescent device 100, and usually quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape according to the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, polysulfone and the like are preferable. In the case of a glass substrate, soda lime glass, non-alkali glass, or the like is used, and the thickness only needs to be sufficient to maintain the mechanical strength. The upper limit value of the thickness is, for example, 2 mm or less, preferably 1 mm or less. The glass material is preferably alkali-free glass because it is better to have less ions eluted from the glass. However, soda lime glass with a barrier coat such as SiO ₂ is also commercially available, so it can be used. it can. Further, the substrate 101 may be provided with a gas barrier film such as a dense silicon oxide film on at least one surface in order to improve the gas barrier property, and a synthetic resin plate, film or sheet having a low gas barrier property is used as the substrate 101. When used, it is preferable to provide a gas barrier film.

<Anode in organic electroluminescence device>
The anode 102 serves to inject holes into the light emitting layer 105. When the hole injection layer 103 and / or the hole transport layer 104 are provided between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through these layers. .

  Examples of the material for forming the anode 102 include inorganic compounds and organic compounds. Examples of inorganic compounds include metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), etc.), halogenated compounds, etc. Examples thereof include metals (such as copper iodide), copper sulfide, carbon black, ITO glass, and nesa glass. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole and polyaniline, and the like. In addition, it can select suitably from the substances currently used as an anode of an organic electroluminescent element, and can use it.

  The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300Ω / □ or less functions as an element electrode. However, since it is now possible to supply a substrate of about 10Ω / □, for example, 100-5Ω / □, preferably 50-5Ω. It is particularly desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 100 to 300 nm.

<Hole injection layer and hole transport layer in organic electroluminescence device>
The hole injection layer 103 plays a role of efficiently injecting holes moving from the anode 102 into the light emitting layer 105 or the hole transport layer 104. The hole transport layer 104 plays a role of efficiently transporting holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating and mixing one kind or two or more kinds of hole injection / transport materials or a mixture of the hole injection / transport material and the polymer binder. Is done. In addition, an inorganic salt such as iron (III) chloride may be added to the hole injection / transport material to form a layer.

  As a hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied. The hole injection efficiency is high, and the injected holes are transported efficiently. It is desirable to do. For this purpose, it is preferable to use a substance that has a low ionization potential, a high hole mobility, excellent stability, and is less likely to generate trapping impurities during production and use.

  As a material for forming the hole injection layer 103 and the hole transport layer 104, a polycyclic fused-ring compound having a skeleton represented by the general formula (1) can be used. The content of the polycyclic fused-ring compound having a skeleton represented by the general formula (1) in the hole injection layer 103 or the hole transport layer 104 is 1 to 100% by weight, more preferably 10 to 100% by weight, particularly 50 -100% by weight, in particular 80-100% by weight is preferred.

  Further, as other materials for forming the hole injection layer 103 and the hole transport layer 104, compounds conventionally used as charge transport materials for holes in photoconductive materials, p-type semiconductors, organic electroluminescent elements are used. Any of known materials used for the hole injection layer and the hole transport layer can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-allylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amine in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4 , 4′-diaminobiphenyl, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4 , 4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl-1,1 -Triphenylamine derivatives such as diamine, 4,4 ', 4 "-tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, stilbene derivatives, phthalocyanine derivatives (metal free, copper phthalocyanine, etc.) ), Pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, heterocyclic compounds such as oxadiazole derivatives, porphyrin derivatives, polysilanes, etc. In polymer systems, polycarbonates and styrene derivatives having the aforementioned monomers in the side chain, Polyvinyl carbazole and polysilane are preferable, but the compound is not particularly limited as long as it is a compound that forms a thin film necessary for manufacturing a light-emitting element, can inject holes from the anode, and can further transport holes.

  It is also known that the conductivity of organic semiconductors is strongly influenced by the doping. Such an organic semiconductor matrix material is composed of a compound having a good electron donating property or a compound having a good electron accepting property. Strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinone dimethane (F4TCNQ) are known for doping of electron donor materials. (For example, the document “M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998)”) and the document “J. Blochwitz, M Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)). M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (22), 3202-3204 (1998). And J. Blochwitz, M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998). These generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material varies considerably. Known matrix substances having hole transporting properties include, for example, benzidine derivatives (TPD and the like), starburst amine derivatives (TDATA and the like), and specific metal phthalocyanines (particularly zinc phthalocyanine ZnPc and the like). 2005-167175).

<Light emitting layer in organic electroluminescent element>
The light emitting layer 105 emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a high emission (fluorescence and / or phosphorescence) efficiency.

  The light emitting layer may be either a single layer or a plurality of layers, each formed of a light emitting material (host material, dopant material), which may be a mixture of a host material and a dopant material or a host material alone. Or either. That is, in each layer of the light emitting layer, only the host material or the dopant material may emit light, or both the host material and the dopant material may emit light. Each of the host material and the dopant material may be one kind or a plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. If the amount of the dopant material is too large, a concentration quenching phenomenon occurs, so that it is preferably used in an amount of 10 to 1% by weight, more preferably 5 to 2% by weight, based on the host material. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

  In addition, the light emitting material of the light emitting element according to this embodiment may be either fluorescent or phosphorescent.

  As a host material, a polycyclic fused ring compound having a skeleton represented by the general formula (1) can be used. The content of the polycyclic fused ring compound having a skeleton represented by the general formula (1) in the light emitting layer 105 as a host material is 1 to 100% by weight, further 10 to 100% by weight, particularly 50 to 100% by weight. In particular, 80 to 100% by weight is preferable.

  Other host materials include, but are not limited to, metal chelated oxinoid compounds such as fused ring derivatives such as anthracene and pyrene, tris (8-quinolinolato) aluminum, which have been known as light emitters. Bisstyryl derivatives such as bisstyryl anthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, For pyrrolopyrrole derivatives and polymer systems, polyphenylene vinylene derivatives, polyparaphenylene derivatives, and polythiophene derivatives are preferably used.

  In addition, as a host material, it can select and use suitably from the compound etc. which were described in the chemical industry June, 2004 issue page 13, and the reference cited up.

  Moreover, the polycyclic fused-ring compound which has the frame | skeleton represented by the said General formula (1) can be used as dopant material. The content of the polycyclic fusedring compound having a skeleton represented by the general formula (1) in the light emitting layer 105 as a dopant material is 1 to 50% by weight, further 1 to 200% by weight, and particularly 1 to 10% by weight. In particular, 1 to 5% by weight is preferable.

  The other dopant material is not particularly limited, and a known compound can be used, and can be selected from various materials according to a desired emission color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene and rubrene, benzoxazole derivatives, benzthiazole derivatives, benzimidazole derivatives, benztriazole derivatives, oxazole derivatives, Bisstyryl derivatives such as oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives and distyrylbenzene derivatives Kaihei 1-245087), bisstyrylarylene derivatives (Japanese Patent Laid-Open No. 2-247278) Isobenzofuran derivatives such as diazaindacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, Dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzthiazolylcoumarin derivatives, 3-benzimidazolylcoumarin derivatives Derivatives, coumarin derivatives such as 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives , Oxobenzanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2, 5-thiadiazolopyrene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, diazaflavin derivatives, and the like.

  Illustratively for each color light, blue to blue-green dopant materials include naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene, indene and other aromatic hydrocarbon compounds and derivatives thereof, furan, pyrrole, thiophene, silole, Aromatic heterocyclic compounds such as 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, naphthyridine, quinoxaline, pyrrolopyridine, thioxanthene And its derivatives, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, thiadiazole, cal Azole derivatives such as sol, oxazole, oxadiazole, triazole and metal complexes thereof, and N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′- Examples thereof include aromatic amine derivatives represented by diamine.

  Examples of the green to yellow dopant material include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene, and the above blue A compound in which a substituent capable of increasing the wavelength such as an aryl group, a heteroaryl group, an arylvinyl group, an amino group, or a cyano group is introduced into the compound exemplified as a blue-green dopant material is also a suitable example.

  Further, examples of the orange to red dopant material include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, rare earth complexes such as Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, 4 -(Dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, quinacridone Derivatives, phenoxazine derivatives, oxazine derivatives, quinazoline derivatives, pyrrolopyridine derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, phenoxazones Conductors and thiadiazolopyrene derivatives, etc. can be used. In addition, the compounds exemplified above as blue to blue-green and green to yellow dopant materials can increase the wavelength of aryl groups, heteroaryl groups, arylvinyl groups, amino groups, cyano groups, etc. A compound into which a substituent is introduced is also a suitable example. Furthermore, a phosphorescent metal complex having iridium represented by tris (2-phenylpyridine) iridium (III) or platinum as a central metal is also a suitable example.

  In addition, as a dopant, it can select and use suitably from the compound etc. which were described in the chemical industry June, 2004 issue page 13, and the reference cited up.

<Electron injection layer and electron transport layer in organic electroluminescence device>
The electron injection layer 107 plays a role of efficiently injecting electrons moving from the cathode 108 into the light emitting layer 105 or the electron transport layer 106. The electron transport layer 106 plays a role of efficiently transporting electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light emitting layer 105. The electron transport layer 106 and the electron injection layer 107 are each formed by laminating and mixing one or more electron transport / injection materials or a mixture of the electron transport / injection material and the polymer binder.

  The electron injecting / transporting layer is a layer that administers electrons injected from the cathode and further transports electrons. It is desirable that the electron injecting electrons have high efficiency and efficiently transport the injected electrons. For this purpose, it is preferable to use a substance that has a high electron affinity, a high electron mobility, excellent stability, and is unlikely to generate trapping impurities during production and use. However, considering the transport balance between holes and electrons, if the role of effectively preventing the holes from the anode from flowing to the cathode side without recombination is mainly played, the electron transport capability is much higher. Even if it is not high, the effect of improving the luminous efficiency is equivalent to that of a material having a high electron transport capability. Therefore, the electron injection / transport layer in this embodiment may include a function of a layer that can efficiently block the movement of holes.

  As a material for forming the electron transport layer 106 and the electron injection layer 107, a polycyclic fused ring compound having a skeleton represented by the general formula (1) can be used. The content of the polycyclic fused-ring compound having a skeleton represented by the general formula (1) in the electron transport layer 106 or the electron injection layer 107 is 1 to 100% by weight, further 10 to 100% by weight, particularly 50 to 100%. % By weight, especially 80 to 100% by weight is preferred.

  Other materials for forming the electron transport layer and the electron injection layer include compounds conventionally used as electron transport compounds in photoconductive materials, and known materials used for the electron injection layer and the electron transport layer of organic electroluminescent devices. Any of these compounds can be selected and used.

  As a material used for the electron transport layer and the electron injection layer, a compound comprising an aromatic ring or a heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, a pyrrole derivative And at least one selected from the condensed ring derivatives thereof and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinones And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include quinolinol complexes such as tris (8-quinolinolato) aluminum, hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. Etc. These materials can be used alone or in combination with different materials. Among them, quinolinol complexes such as tris (8-quinolinolato) aluminum, anthracene derivatives such as 9,10-bis (2-naphthyl) anthracene, styryl aromatic ring derivatives such as 4,4′-bis (diphenylethenyl) biphenyl, Carbazole derivatives such as 4,4′-bis (N-carbazolyl) biphenyl and 1,3,5-tris (N-carbazolyl) benzene are preferably used from the viewpoint of durability.

  Specific examples of other electron transfer compounds include pyridine derivatives, phenanthroline derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives, thiophene derivatives, triazole derivatives, thiadiazole derivatives, metal complexes of oxine derivatives, quinolinol metal complexes, Quinoxaline derivatives, polymers of quinoxaline derivatives, benzazole compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives, imidazopyridine derivatives, borane derivatives, benzimidazole derivatives, benzoxazole derivatives, benz Thiazole derivatives, quinoline derivatives, oligopyridine derivatives such as bipyridine and terpyridine, naphthyridine derivatives, aldazine derivatives, Such as Susuchiriru derivatives.

Among them, pyridine derivatives (for example, 2,5-bis (6 ′-(2 ′, 2 ″ -bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (hereinafter abbreviated as PyPySPyPy), 9,10 -Di (2 ', 2 "-bipyridyl) anthracene, 2,5-di (2', 2" -bipyridyl) thiophene, 2,5-di (3 ', 2 "-bipyridyl) thiophene, 6'6"- Di (2-pyridyl) 2,2 ′: 4 ′, 3 ″: 2 ″, 2 ″ -quaterpyridine, etc.), phenanthroline derivatives (for example, 4,7-diphenyl-1,10-phenanthroline, 2,9- Dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10-di (1,10-phenanthroline-2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, , 3, -Tri (1,10-phenanthroline-5-yl) benzene, 9,9'-difluoro-bis (1,10-phenanthroline-5-yl), bathocuproine or 1,3-bis (2-phenyl-1,10 -Phenanthroline-9-yl) benzene), quinolinol-based metal complexes (for example, tris (8-hydroxyquinoline) aluminum (hereinafter abbreviated as Alq3), bis (10-hydroxybenzo [h] quinoline) beryllium, tris Imidazoles such as (4-methyl-8-hydroxyquinoline) aluminum, bis (2-methyl-8-hydroxyquinoline)-(4-phenylphenol) aluminum), tris (N-phenylbenzimidazol-2-yl) benzene Derivative 1,3-bis [(4-tert-butylphenyl) 1,3,4- Oxadiazole derivatives such as oxadiazolyl] phenylene, triazole derivatives such as N-naphthyl-2,5-diphenyl-1,3,4-triazole, 2,2′-bis (benzo [h] quinolin-2-yl)- Benzoquinoline derivatives such as 9,9′-spirobifluorene, terpyridine derivatives such as 1,3-bis (4 ′-(2,2 ′: 6′2 ″ -terpyridinyl)) benzene, bis (1-naphthyl)- Naphthyridine derivatives such as 4- (1,8-naphthyridin-2-yl) phenylphosphine oxide are preferred.
In particular, when a pyridine derivative or a phenanthroline derivative is used for the electron transport layer or the electron injection layer, low voltage and high efficiency can be realized.

  A case where an organic phosphor having a phenanthroline skeleton is used for the electron transport layer will be described. In order to obtain stable light emission over a long period of time, a material excellent in thermal stability and thin film formation is desired, and among organic phosphors having a phenanthroline skeleton, the substituent itself has a three-dimensional structure, Those having a three-dimensional structure by steric repulsion with a phenanthroline skeleton or adjacent substituents, or those having a plurality of phenanthroline skeletons linked to each other are preferred. Furthermore, when linking a plurality of phenanthroline skeletons, a compound containing a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, or a substituted or unsubstituted aromatic heterocycle in the linking unit is more preferable.

<Cathode in organic electroluminescence device>
The cathode 108 serves to inject electrons into the light emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.

  The material for forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, but the same material as that for forming the anode 102 can be used. Among them, metals such as tin, magnesium, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, tin, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys (magnesium- Silver alloys, magnesium-indium alloys, aluminum-lithium alloys such as lithium fluoride / aluminum) are preferred. Lithium, sodium, potassium, cesium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics. However, these low work function metals are generally unstable in the atmosphere. For example, the organic layer is doped with a small amount of lithium, cesium, or magnesium (1 nm or less in vacuum vapor deposition thickness gauge display). Although a method using a highly stable electrode can be given as a preferred example, it is particularly limited to these because inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide can also be used. It is not something.

  Further, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride Lamination of hydrocarbon polymer compounds and the like is a preferred example. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam, sputtering, ion plating, and coating.

<Binder that may be used in each layer>
The materials used for the hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer alone, but as a polymer binder, polyvinyl chloride, polycarbonate, Polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfone, polyamide, ethyl cellulose, vinyl acetate, ABS resin, Disperse in solvent-soluble resins such as polyurethane resin, curable resins such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, etc. Possible it is.

<Method for producing organic electroluminescent element>
Each layer constituting the organic electroluminescent element is formed by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination method, printing method, spin coating method or casting method, coating method, etc. It can be formed by using a thin film. The thickness of each layer formed in this way is not particularly limited and can be appropriately set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like. When a thin film is formed using a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the intended crystal structure and association structure of the film, and the like. Deposition conditions generally include boat heating temperature of 50 to 400 ° C., vacuum degree of 10 ⁻⁶ to 10 ⁻³ Pa, deposition rate of 0.01 to 50 nm / second, substrate temperature of −150 to + 300 ° C., and film thickness of 2 nm to 5 μm. It is preferable to set appropriately within the range.

  Next, as an example of a method for producing an organic electroluminescent device, an organic electric field composed of an anode / hole injection layer / hole transport layer / a light emitting layer composed of a host material and a dopant material / electron transport layer / electron injection layer / cathode. A method for manufacturing a light-emitting element will be described. A thin film of an anode material is formed on a suitable substrate by vapor deposition or the like to produce an anode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-evaporated on this to form a thin film to form a light emitting layer. An electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by vapor deposition. By forming it as a cathode, a desired organic electroluminescent element can be obtained. In the preparation of the above-described organic electroluminescence device, the order of preparation may be reversed, and the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode may be fabricated in this order. Is possible.

  When a DC voltage is applied to the organic electroluminescent device thus obtained, the anode may be applied with a positive polarity and the cathode with a negative polarity. When a voltage of about 2 to 40 V is applied, the organic electroluminescent device is transparent or translucent. Luminescence can be observed from the electrode side (anode or cathode, and both). The organic electroluminescence device emits light when a pulse current or an alternating current is applied. The alternating current waveform to be applied may be arbitrary.

<Application examples of organic electroluminescent devices>
The present invention can also be applied to a display device provided with an organic electroluminescent element or a lighting device provided with an organic electroluminescent element.
A display device or an illuminating device including an organic electroluminescent element can be manufactured by a known method such as connecting the organic electroluminescent element according to the present embodiment and a known driving device, such as direct current driving, pulse driving, or alternating current. It can be driven by appropriately using a known driving method such as driving.

  Examples of the display device include a panel display such as a color flat panel display, and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Gazette, Japanese Patent Application Laid-Open No. 2004-281086, etc.). Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.

  A matrix means a pixel in which pixels for display are two-dimensionally arranged such as a lattice or a mosaic, and displays a character or an image with a set of pixels. The shape and size of the pixel are determined by the application. For example, a square pixel with a side of 300 μm or less is usually used for displaying images and characters on a personal computer, monitor, TV, and a pixel with a side of mm order for a large display such as a display panel. become. In monochrome display, pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. The matrix driving method may be either a line sequential driving method or an active matrix. The line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.

  In the segment method (type), a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light. For example, the time and temperature display in a digital clock or a thermometer, the operation state display of an audio device or an electromagnetic cooker, the panel display of an automobile, and the like can be mentioned.

  Examples of the illuminating device include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, Japanese Patent Application Laid-Open Nos. 2003-257621, 2003-277741, and 2004-119211). Etc.) The backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, a sign, and the like. In particular, as a backlight for liquid crystal display devices, especially personal computers for which thinning is an issue, considering that conventional methods are made of fluorescent lamps and light guide plates, it is difficult to reduce the thickness. The backlight using the light emitting element according to the embodiment is thin and lightweight.

  Hereinafter, each example will be shown to describe the present invention in more detail, but the present invention is not limited thereto.

<Production Example of Polycyclic Fused Compound>
A polycyclic fused ring compound represented by the following formula (2-1) A method for synthesizing a polycyclic fused ring compound represented by the following formula (2-1) will be described.

Reaction (1): Synthesis of 1-ethoxydimethylsilyl-2-trimethylsilylethynylbenzene 1-Bromo-2-trimethylsilylethynylbenzene (15 g, 60 mmol) in an ether solution (200 mL) in n-butyllithium in hexane (1.6 mol) / L, 38 mL, 60 mmol) was added dropwise at −78 ° C., and (N, N-diethylamino) dimethylsilyl chloride (13 g, 80 mmol) was added. The mixture was stirred for 10 hours while slowly warming to room temperature, ethanol (60 mL) and ammonium chloride (6.7 g, 126 mmol) were added, and the mixture was stirred for 5 hours.
The reaction mixture was filtered to remove insolubles, and the filtrate was concentrated and separated and purified by silica gel column chromatography and distillation to collect 1-ethoxydimethylsilyl-2-trimethylsilylethynylbenzene (15 g, 53 mmol). The rate was 88%.

Reaction (2): Synthesis of 1-ethoxydimethylsilyl-2-ethynylbenzene 1-ethoxydimethylsilyl-2-trimethylsilylethynylbenzene (15 g, 53 mmol), potassium carbonate (0.73 g, 5.3 mmol), ethanol (100 mL) , THF (100 mL) was stirred at room temperature overnight.
The reaction mixture was filtered through celite to remove insolubles. The filtrate was concentrated and then separated and purified by silica gel column chromatography to obtain 1-ethoxydimethylsilyl-2-ethynylbenzene (9.9 g, 49 mmol) in a yield of 92%.

Reaction (3): Synthesis of 1- (2-bromophenylethynyl) -2-ethoxydimethylsilylbenzene 1-ethoxydimethylsilyl-2-ethynylbenzene (2.2 g, 11 mmol) was converted to 1-bromo-2-iodobenzene. (2.8 g, 10 mmol), palladium chloride bistriphenylphosphine complex (70 mg, 0.10 mmol), copper iodide (38 mg, 0.20 mmol), triethylamine (25 mL), and the mixture was stirred at room temperature for 12 hours.
The reaction mixture was filtered through celite to remove insolubles. The filtrate was concentrated and separated and purified by silica gel column chromatography to obtain 1- (2-bromophenylethynyl) -2-ethoxydimethylsilylbenzene (3.4 g, 9.5 mmol) in a yield of 95%. It was.

Reaction (4): Synthesis of the polycyclic fused ring compound represented by the above formula (2-1) 1- (2-bromophenylethynyl) -2-ethoxydimethylsilylbenzene (0.18 g, 0.50 mmol) in THF A pentane solution of t-butyllithium (1.42 mol / L, 0.70 mL, 1.0 mmol) was added dropwise to the solution (1 mL) at -78 ° C. After stirring for 3 hours while maintaining the temperature at -78 ° C, a toluene solution (1 mL) of sulfur (16 mg, 0.50 mmol) was added, and the mixture was stirred for 6 hours while slowly warming to room temperature.
The solvent was distilled off under reduced pressure, ether was added, and insoluble matters were removed by filtration. The filtrate was concentrated and then separated and purified by silica gel column chromatography to obtain the target compound (80 mg, 0.30 mmol) in a yield of 60%.

The physical properties of the target compound were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.53 (s, 6H), δ 7.25-7.44 (m, 4H), δ 7.50-7.53 (m, 1H), δ 7.58-7. 60 (m, 1H), δ 7.74-7.76 (m, 1H), δ 7.88-7.90 (m, 1H)
UV-vis maximum absorption wavelength (THF solution): λmax = 322 nm
Maximum fluorescence wavelength (THF solution): λmax = 383 nm

A polycyclic fused ring compound represented by the following formula (2-2) A method for synthesizing a polycyclic fused ring compound represented by the following formula (2-2) will be described.

  M-Chloroperbenzoic acid (72 mg, 0.32 mmol) and dichloromethane (30 mL) were added to the compound represented by the above formula (2-1) (43 mg, 0.16 mmol), and the mixture was stirred at room temperature for 6 days. The reaction mixture was separated and purified by silica gel column chromatography to obtain the target compound (39 mg, 0.13 mmol) in a yield of 80%.

The physical properties of the target compound were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.57 (s, 6H), δ 7.29-7.65 (m, 6H), δ 7.71-7.76 (m, 2H)
UV-vis maximum absorption wavelength (THF solution): λmax = 366 nm
Maximum fluorescence wavelength (THF solution): λmax = 447 nm

A polycyclic fused ring compound represented by the following formula (3-1 ′) A method for synthesizing a polycyclic fused ring compound represented by the following formula (3-1 ′) will be described.

Reaction (1): Synthesis of 1,4-dibromo-2,5-bis (2-ethoxydimethylsilylphenylethynyl) benzene 1-Ethoxydimethylsilyl-2-ethynylbenzene (7.4 g, 36 mmol) was converted to 1,4 -Dibromo-2,5-diiodobenzene (9.3 g, 19 mmol), palladium chloride bistriphenylphosphine complex (0.27 g, 0.38 mmol), copper iodide (0.14 g, 0.76 mmol), triethylamine (30 mL) ), THF (60 mL), and stirred at room temperature for 24 hours.
The reaction mixture was filtered through celite to remove insolubles. The filtrate was concentrated and purified by silica gel column chromatography and recrystallization to obtain 1,4-dibromo-2,5-bis (2-ethoxydimethylsilylphenylethynyl) benzene (4.9 g, 7.6 mmol). Was obtained in a yield of 40%.

Reaction (2): Synthesis of polycyclic fused ring compound represented by the above formula (3-1 ′) 1,4-dibromo-2,5- (2-ethoxydimethylsilylphenylethynyl) benzene (0.70 g, 1 0.1 mmol) in THF (5 mL) was added dropwise a pentane solution of t-butyllithium (1.46 mol / L, 3.3 mL, 4.8 mmol) at -78 ° C. After stirring for 1 hour while maintaining the temperature at −78 ° C., a toluene solution (5 mL) of sulfur (71 mg, 2.2 mmol) was added, and the mixture was stirred for 9 hours while slowly warming to room temperature. A saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with chloroform. The obtained organic layer was dried over anhydrous magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained mixture was washed with hexane, ethanol, and toluene to obtain the target compound (0.14 g, 0.31 mmol) in a yield of 28%.

The physical properties of the target compound were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.57 (s, 12H), δ 7.25-7.31 (m, 2H), δ 7.39-7.45 (m, 2H), δ 7.50-7. 53 (m, 2H), δ 7.59-7.61 (m, 2H), δ 8.19 (s, 2H)
UV-vis maximum absorption wavelength (THF solution): λmax = 401 nm
Maximum fluorescence wavelength (THF solution): λmax = 408 nm, 433 nm, 458 nm

A polycyclic fused ring compound represented by the following formula (3-1 ″) A method for synthesizing a polycyclic fused ring compound represented by the following formula (3-1 ″) will be described.

M-Chloroperbenzoic acid (190 mg, 1.1 mmol) and dichloromethane (15 mL) were added to the compound represented by the above formula (3-1 ′) (50 mg, 0.11 mmol), and the mixture was stirred at room temperature for 5 days.
Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with dichloromethane. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained mixture was separated and purified using GPC to obtain the target compound (25 mg, 0.050 mol) in a yield of 45%.

The physical properties of the target compound were as follows.
¹ H-NMR (CDCl ₃ ): δ 0.62 (s, 12H), δ 7.40-7.55 (m, 4H), δ 7.68 (s, 2H), δ 7.65-7.68 (m, 2H), δ 7.72-7.75 (m, 2H)
UV-vis maximum absorption wavelength (THF solution): λmax = 414 nm
Maximum fluorescence wavelength (THF solution): λmax = 530 nm

The polycyclic fused ring compound represented by the following formula (4-1) A method for synthesizing the polycyclic fused ring compound represented by the following formula (4-1) will be described.

Reaction (1): Synthesis of diethyl 2,5-bis (benzo [b] thiophen-2-yl) diethyl terephthalate Diethyl 2,5-dibromoterephthalate (3.6 g, 9.4 mmol), 2-benzo [b] Thiopheneboronic acid (5.0 g, 28 mmol), palladium acetate (21 mg, 0.094 mmol), 2 ′, 6′-dimethoxybiphenyl-2-yldicyclohexylphosphine (39 mg, 0.094 mmol), potassium phosphate (12 g, 56 mmol) ), Water (1.0 g, 56 mmol), and THF (20 mL) were stirred at room temperature overnight.
Water was added to the reaction mixture and extracted with toluene. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained mixture was separated and purified by silica gel column chromatography to obtain diethyl 2,5-bis (benzo [b] thiophen-2-yl) terephthalate (4.2 g, 8.6 mmol) in a yield of 93%. Obtained.

Reaction (2): Synthesis of 1,4-bis (benzo [b] thiophen-2-yl) -2,5-bis (hydroxydiphenylmethyl) benzene Bromobenzene (3.9 g, 25 mmol) in THF (25 mL) After dropwise addition of a hexane solution of n-butyllithium (1.6 mol / L, 15 mL, 25 mmol) at −78 ° C., diethyl 2,5-bis (benzo [b] thiophen-2-yl) terephthalate (2 0.0 g, 4.1 mmol) was added, and the mixture was stirred overnight while slowly warming to room temperature.
A saturated ammonium chloride solution was added to the reaction mixture, followed by filtration. The resulting white solid was washed with water and ethanol, and 1,4-bis (benzo [b] thiophen-2-yl) -2,5-bis (Hydroxydiphenylmethyl) benzene (2.7 g, 3.9 mmol) was obtained with a yield of 94%.

Reaction (3): Synthesis of polycyclic fused ring compound represented by the above formula (4-1) 1,4-bis (benzo [b] thiophen-2-yl) -2,5-bis (hydroxydiphenylmethyl) Boron trifluoride diethyl ether complex (0.20 mL, 1.6 mmol) was added dropwise to a dichloromethane solution (50 mL) of benzene (0.50 g, 0.71 mmol) at room temperature. After stirring at room temperature for 2 hours, ethanol (100 mL) was added, and the mixture was further stirred at room temperature for 13 hours.
The reaction mixture was filtered, and the resulting mixture was washed with ethanol to obtain the target compound (0.46 g, 0.70 mmol) in a yield of 98%.

The physical properties of the target compound were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.20-7.37 (m, 24H), δ 7.46-7.55 (m, 2H), δ 7.60 (s, 2H), 7.79-7. 87 (m, 2H)
UV-vis maximum absorption wavelength (THF solution): λmax = 395 nm
Maximum fluorescence wavelength (THF solution): λmax = 403 nm, 426 nm

A polycyclic fused ring compound represented by the following formula (4-2) A method for synthesizing a polycyclic fused ring compound represented by the following formula (4-2) will be described.

  M-Chloroperbenzoic acid (0.27 g, 1.2 mmol) and dichloromethane (25 mL) are added to the compound represented by the above formula (4-1) (0.18 g, 0.27 mmol) and stirred at room temperature for 2 days. did. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with dichloromethane. The obtained organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The obtained mixture was washed with ethanol to obtain the target compound (0.19 g, 0.25 mmol) in a yield of 94%.

The physical properties of the target compound were as follows.
¹ H-NMR (CDCl ₃ ): δ 7.16-7.20 (m, 2H), δ 7.30-7.45 (m, 24H), 7.68-7.74 (m, 4H)
UV-vis maximum absorption wavelength (THF solution): λmax = 430 nm
Maximum fluorescence wavelength (THF solution): λmax = 452 nm, 465 nm

<Examples using polycyclic fused-ring compounds as materials for organic electroluminescent elements>
The electroluminescent element according to Example 1 and the electroluminescent element according to Comparative Example 1 were manufactured, and the luminance (cd / m ² ), current density (mA / cm ² ), and luminous efficiency (Lm) when a DC voltage of 5 V was applied, respectively. / W), current efficiency (cd / A), emission wavelength (nm), and chromaticity (x, y) were measured. Hereinafter, examples and comparative examples will be described in detail.

Table 1 below shows the material structure of each layer in the electroluminescent device according to Example 1 and the electroluminescent device according to Comparative Example 1.

In Table 1, Compound 1 is a polycyclic fused ring compound as a material for an organic electroluminescence device, and is a compound represented by the above formula (4-1).
In Table 1, “CuPc” is copper phthalocyanine, “NPD” is N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine, “MSB” is 1,4-bis (2-methyl) Styryl) benzene and “ETM1” are 1,1-dimethyl-2,5-bis (2,2′-bipyridin-6-yl) -3,4-dimesitylsilole, each having the following chemical structural formula Have.

<Example 1>
A transparent support substrate was obtained by depositing ITO on a glass substrate to a thickness of 150 nm. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus, and a molybdenum vapor deposition boat containing “CuPc”, a molybdenum vapor deposition boat containing “NPD”, and a molybdenum vapor deposition boat containing compound 1 A molybdenum vapor deposition boat containing “ETM1”, a molybdenum vapor deposition boat containing lithium fluoride, and a tungsten vapor deposition boat containing aluminum were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 1 × 10 ⁻³ Pa, first, a vapor deposition boat containing “CuPc” is heated and vapor-deposited to a film thickness of 20 nm to form a hole injection layer, and then “NPD The evaporation boat containing “is heated and evaporated to a film thickness of 30 nm to form a hole transport layer. Next, the evaporation boat containing the compound 1 was heated and evaporated to a film thickness of 35 nm to form a light emitting layer. Next, the evaporation boat containing “ETM1” was heated and evaporated to a film thickness of 15 nm to form an electron transport layer. The deposition rate of each layer was 0.001 to 3.0 nm / sec.

  Thereafter, the evaporation boat containing lithium fluoride is heated to deposit at a deposition rate of 0.003 to 0.01 nm / second so that the film thickness becomes 0.5 nm, and then the evaporation boat containing aluminum is heated. The cathode was formed by vapor deposition at a vapor deposition rate of 0.1 to 1 nm / second so that the film thickness was 100 nm, and an electroluminescent element was obtained.

Using the ITO electrode as the anode and the lithium fluoride / aluminum electrode as the cathode, the characteristics when a DC voltage of 5 V was applied were measured. The luminance was 100 (cd / m ² ), the current density was 16 (mA / cm ² ), and the luminous efficiency was 0.37. (Lm / W), current efficiency 0.61 (cd / A), emission wavelength 440 (nm), and chromaticity (0.15, 0.08).

<Comparative Example 1>
An electroluminescent device was obtained in exactly the same manner as in Example 1 except that “MSB” was used instead of Compound 1 as the light emitting layer material used in Example 1. When a direct current voltage of 5 V was applied using an ITO electrode as an anode and a lithium fluoride / aluminum electrode as a cathode, a current with a current density of 0.1 (mA / cm ² ) flowed, but no light emission was seen from the device. .

  According to a preferred aspect of the present invention, it is possible to provide an organic electroluminescent element having better performance in light emission efficiency and current efficiency, a display device including the same, a lighting device including the same, and the like.

It is a schematic sectional drawing which shows the organic electroluminescent element which concerns on this embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 100 Organic electroluminescent 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

Claims (26)

A polycyclic condensed ring compound having a skeleton represented by the following general formula (1).
(In the formula (1) , (1A-1) or (1A-2) ,
One of A ¹ and A ² is unsubstituted sulfur or SO ₂ , and the other of A ¹ and A ² is a group represented by the formula (1A-1), or A ¹ is unsubstituted a sulfur or SO _2, ^{a 2} is a group represented by the formula (1A-2),
R ¹ and R ² are each independently an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted alkoxy, or an optionally substituted. Alkylthio, optionally substituted aryl, optionally substituted aryloxy, optionally substituted arylthio, optionally substituted arylalkyl, optionally substituted arylalkoxy, optionally substituted Good arylalkylthio, optionally substituted arylalkenyl, optionally substituted arylalkynyl, optionally substituted boryl, optionally substituted amino, optionally substituted silyl, substituted May be substituted silyloxy, optionally substituted arylsulfonyloxy, Are alkyl sulfates also be sulfonyl oxy, aralkyl optionally substituted, heteroaryl optionally substituted, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted alkoxy, substituted Alkylthio, which may be substituted, aryl which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, arylalkyl which may be substituted, arylalkoxy which may be substituted, substituted Arylalkylthio which may be substituted, arylalkenyl which may be substituted, arylalkynyl which may be substituted, amino which may be substituted, silyl which may be substituted, silyloxy which may be substituted, substituted Optionally substituted arylsulfonyloxy, optionally substituted al Rusuru sulfonyl oxy, aralkyl optionally substituted, optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
n is each independently 0, 1, 2, 3 or 4;
m is 0, 1 or 2;
p is a value of 0 or 1, but p is 1 when A ¹ is unsubstituted sulfur or SO ₂ and A ² is a group represented by the formula (1A-2) . ) The polycyclic fused-ring compound according to claim 1 represented by the following general formula (2).
(In the formula (2) or (2A),
R ¹ are each independently alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, an optionally substituted silyl, substituted Optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl ,
R ³ and R ⁴ are each independently hydrogen, alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, substituted Silyl , optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
each n is independently 0 , 1 or 2 ,
One of A ¹ and A ² is unsubstituted sulfur or SO ₂ , and the other of A ¹ and A ² is a group represented by the formula (2A). ) R ³ and ^{R 4} are each independently hydrogen or a alkyl which may be substituted having 1 to 20 carbon atoms,
n is 0,
The condensed polycyclic compound according to claim 2 . R ³ and ^{R 4} are each independently methyl, ethyl, propyl, butyl, hexyl or octyl,
n is 0,
The condensed polycyclic compound according to claim 2 . Formula (2-1) or (2-2) condensed polycyclic compound according to claim 2 represented by.
The polycyclic fused-ring compound of Claim 1 represented by following General formula (3).
(In the formula (3) or (3A),
R ¹ and R ² are each independently alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, may be substituted Silyl , optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl ;
R ³ and R ⁴ are each independently hydrogen, alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, substituted Silyl , optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
m is 0, 1 or 2, n is each independently 0 , 1 or 2 ,
One of A ¹ and A ² is unsubstituted sulfur or SO ₂ , and the other of A ¹ and A ² is a group represented by the formula (3A). ) R ³ and ^{R 4} are each independently hydrogen or a alkyl which may be substituted having 1 to 20 carbon atoms,
m is 0 and n is 0.
The condensed polycyclic compound according to claim 6 . R ³ and ^{R 4} are each independently methyl, ethyl, propyl, butyl, hexyl or octyl,
m is 0 and n is 0.
The condensed polycyclic compound according to claim 6 . Formula (3-1) or the polycyclic fused ring compound according to claim 6 represented by (3-2).
The polycyclic fused ring compound according to claim 1 represented by the following general formula (4).
(In the formula (4) or (4A),
R ¹ and R ² are each independently alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, may be substituted Silyl , optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl ;
R ³ and R ⁴ are each independently hydrogen, optionally substituted alkyl , optionally substituted aryl , optionally substituted heteroaryl, optionally substituted cycloalkyl, cyano, Nitro or hydroxyl,
m is 0, 1 or 2, n is each independently 0 , 1 or 2 ,
A ¹ is unsubstituted sulfur or SO ₂ , and A ² is a group represented by the formula (4A). ) R ³ and R ⁴ are each independently hydrogen, alkyl which may be substituted having 1 to 20 carbon atoms, or an aryl optionally substituted 5 to 30 carbon atoms,
m is 0 and n is 0.
The polycyclic fused ring compound according to claim 10 . R ³ and ^{R 4} are each independently hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, phenyl or naphthyl,
m is 0 and n is 0.
The polycyclic fused ring compound according to claim 10 . Formula (4-1) or (4-2) condensed polycyclic compound according to claim 10 which is represented by.
(In the formula, “Ph” is a phenyl group.)
It claims 1 to n dimerization condensed polycyclic compounds described in 13, which are n-mer of condensed polycyclic compounds. However, n is 2-8. The n-merized polycyclic fused ring compound according to claim 14 , wherein n is 2. Halogen synthesis intermediate is reacted with an organometallic base condensed polycyclic compound represented by the following general formula (5) - was metallated by metal exchange and the resulting anion to claim 2 by trapping with sulfur A method for producing a polycyclic fused ring compound, which obtains the polycyclic fused ring compound to be described.
(In Formula (5),
X is hydrogen, halogen, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryloxy, or optionally substituted arylthio, or optionally substituted silyl. Yes,
Y is Cl, Br or I;
R ¹ are each independently alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, an optionally substituted silyl, substituted Optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl ,
R ³ and R ⁴ are each independently hydrogen, alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, substituted Silyl , optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
n is each independently 0 , 1 or 2 . ) R ³ and ^{R 4} are each independently hydrogen or a alkyl which may be substituted having 1 to 20 carbon atoms,
n is 0,
The manufacturing method of the polycyclic fused-ring compound of Claim 16 . R ³ and ^{R 4} are each independently methyl, ethyl, propyl, butyl, hexyl or octyl,
n is 0,
The manufacturing method of the polycyclic fused-ring compound of Claim 16 . By reacting a synthetic intermediate of a polycyclic fused ring compound represented by the following general formula (6) or (7) with an organometallic base, metalating by halogen-metal exchange, and then capturing the generated anion with sulfur The manufacturing method of the polycyclic fused-ring compound which obtains the polycyclic fused-ring compound described in Claim 6 .
(In the formulas (6) and (7),
X is hydrogen, halogen, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted aryloxy, or optionally substituted arylthio, or optionally substituted silyl. Yes,
Y is Cl, Br or I;
R ¹ and R ² are each independently alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, may be substituted Silyl , optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl ;
R ³ and R ⁴ are each independently hydrogen, alkyl optionally substituted, optionally substituted alkoxy, aryl which may be substituted, amino which may be substituted, substituted Silyl , optionally substituted heteroaryl, optionally substituted cycloalkyl, halogen, cyano, nitro or hydroxyl,
m is 0, 1 or 2, and n is independently 0 , 1 or 2 . ) R ³ and ^{R 4} are each independently hydrogen or a alkyl which may be substituted having 1 to 20 carbon atoms,
m is 0 and n is 0.
The manufacturing method of the polycyclic fused-ring compound of Claim 19 . R ³ and ^{R 4} are each independently methyl, ethyl, propyl, butyl, hexyl or octyl,
m is 0 and n is 0.
The manufacturing method of the polycyclic fused-ring compound of Claim 19 . The organic electroluminescent element material containing the polycyclic fused-ring compound or n-merized polycyclic fused-ring compound in any one of Claims 1 thru | or 15 . An organic electroluminescent device comprising a pair of electrodes comprising an anode and a cathode, and one or more layers disposed between the pair of electrodes and comprising the material for an organic electroluminescent device according to claim 22 . The organic electroluminescent element according to claim 23 , wherein the one or more layers containing the material for an organic electroluminescent element is a light emitting layer. The display apparatus provided with the organic electroluminescent element of Claim 23 or 24 . The illuminating device provided with the organic electroluminescent element of Claim 23 or 24 .