KR20200078683A - Azadibenzofurans for electronic applications - Google Patents

Abstract

(I)의 화합물; 그의 제조 방법; 및 전자 장치, 특히 전계발광 장치에서의 그의 용도에 관한 것이다. 전계발광 장치에서 인광 방출체를 위한 호스트 물질로서 사용되는 경우에, 화학식 (I)의 화합물은 전계발광 장치의 개선된 효율, 안정성, 제조성 또는 스펙트럼 특성을 제공할 수 있다.The present invention is substituted by benzimidazo[1,2-a]benzimidazo-5-yl and/or benzimidazo[1,2-a]benzimidazo-2,5-ylene group, substituent B Formulas characterized in that at least one of ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ and B ⁸ represents N

Compound of (I); Its manufacturing method; And its use in electronic devices, particularly electroluminescent devices. When used as a host material for a phosphorescent emitter in an electroluminescent device, the compound of formula (I) may provide improved efficiency, stability, manufacturability or spectral properties of the electroluminescent device.

Description

Azadibenzofuran for electronic applications {AZADIBENZOFURANS FOR ELECTRONIC APPLICATIONS}

The present invention relates to compounds of formula (I), methods for their preparation, and their use in electronic devices, in particular electroluminescent devices. When used as a hole transport material in an electroluminescent device, the compound of formula (I) can provide improved efficiency, stability, manufacturability or spectral properties of the electroluminescent device.

의 합성을 기재하고 있다.See Khan, Misbahul Ain; Ribeiro, Vera Lucia Teixeira, Pakistan Journal of Scientific and Industrial Research 43 (2000) 168-170, is a trialkyl phosphite of 1-(o-nitrophenyl)- and 1-(o-azidophenyl)benzimidazole- Benzimidazole[1,2-a]benzimidazole by induced deoxygenation and thermal decomposition

Synthesis of is described.

Pedro Molina et al. Tetrahedron (1994) 10029-10036] is a Witztig-type reaction of bis(iminophosphorans) derived from bis(2-aminophenyl)amine with 2 equivalents of isocyanate, Benzimidazo[1,2 ,a] It has been reported to provide benzimidazole derivatives directly.

See Kolesnikova, I. V.; Zhurnal Organicheskoi Khimii 25 (1989) 1689-95] is 5H-benzimidazole[1,2-a]benzimidazole 1,2,3,4,7,8,9,10-octafluoro-5-( 2,3,4,5,6-pentafluorophenyl).

의 합성을 기재하고 있다.Achour, Reddouane; Zniber, Rachid, Bulletin des Societes Chimiques Belges 96 (1987) 787-92] is a benzimidazenzobenzimidazole prepared from a benzimidazolinone derivative.

Synthesis of is described.

의 합성을 기재하고 있다.See Hubert, Andre J.; Reimlinger, Hans, Chemische Berichte 103 (1970) 2828-35] is benzimidazobenzimidazole

Synthesis of is described.

WO2011160757 is an anode, a cathode, and a chemical formula

의 화합물 (여기서, X는 단일 결합일 수 있고, L은 2가 기일 수 있음)을 함유하는 적어도 1개의 유기 층을 포함하는 전자 장치에 관한 것이다. 하기 4H-이미다조[1,2-a]이미다졸 화합물이 명시적으로 개시되어 있다:

It relates to an electronic device comprising at least one organic layer containing a compound, wherein X may be a single bond, L may be a divalent group. The following 4H-imidazo[1,2-a]imidazole compounds are explicitly disclosed:

의 화합물에 대한 고효율 구리-촉매화 합성에 대해 개시하고 있으며, 여기서 화학식

의 화합물을 승온에서 m-크실렌 중 아세트산구리 (Cu(OAc)₂)/PPh₃/1,10-페나트롤린/아세트산나트륨 및 산소 (1 atm)의 존재 하에 반응시킨다 [웹 상에 공개됨: 2011년 12월 29일]. 특히, 하기 화합물이 기재된 합성 방법에 의해 제조될 수 있다:[X. Wang et al. Org. Lett. 14 (2012) 452-455] is a chemical formula

High-efficiency copper-catalyzed synthesis for compounds of

The compound of is reacted at elevated temperature in the presence of copper acetate (Cu(OAc) ₂ )/PPh ₃ /1,10-phenatroline/sodium acetate and oxygen (1 atm) in m-xylene [published on the web: 2011 December 29]. In particular, the following compounds can be prepared by the synthetic methods described:

, 예컨대 예를 들어

, 그의 제조 방법, 및 전자 장치, 특히 전계발광 장치에서의 그의 용도에 관한 것이다.WO2012/130709 is 4H-imidazole [1,2-a]imidazole,

For example,

, Its manufacturing method, and its use in electronic devices, particularly electroluminescent devices.

(여기서, X⁶은 -N=이고 X⁷은 -NR⁶-이거나, 또는 X⁷은 =N-이고 X⁶은 -NR⁶-이고, R⁶은 화학식

의 기임)의 4H-이미다조[1,2-a]이미다졸; 그의 제조 방법; 및 전자 장치, 특히 전계발광 장치에서의 그의 용도를 기재하고 있다.WO2013/068376 is the chemical formula

(Where X ⁶ is -N= and X ⁷ is -NR ⁶ -, or X ⁷ is =N- and X ⁶ is -NR ⁶ -, and R ⁶ is the formula

Of 4)-imidazo[1,2-a]imidazole); Its manufacturing method; And its use in electronic devices, particularly electroluminescent devices.

의 화합물, 그의 제조 방법, 및 전자 장치, 특히 전계발광 장치에서의 그의 용도에 관한 것이다. 2,5-이치환된 벤즈이미다조[1,2-a]벤즈이미다졸 유도체가 인광 방출체를 위한 적합한 정공 수송 물질 또는 호스트 물질이다.PCT/EP2013/064395 is the chemical formula

Compounds, methods for their preparation, and their use in electronic devices, in particular electroluminescent devices. The 2,5-disubstituted benzimidazole[1,2-a]benzimidazole derivatives are suitable hole transport materials or host materials for phosphorescent emitters.

US20090134784 provides carbazole-containing compounds. In particular, the compound is an oligocarbazole-containing compound having an asymmetric structure. The compound can be substituted with azadibenzofuranyl, and is useful as a host in the emitting layer of an organic light emitting device.

은 호스트 및 여기자 차단 물질로서 사용된다.WO2010028262 relates to a white phosphorescent organic light emitting device. The following compound

Is used as a host and exciton blocking material.

(여기서, X₁ 및 X₂ 중 하나는 질소이고, X₁ 및 X₂ 중 나머지는 탄소이고, Y는 S 또는 O임)을 갖는 아미노-아릴티오 피리딘 중간체의 아세트산 용액을 tBuONO로 처리하여 화학식

(여기서, R₁ 및 R₂는 모노, 디, 트리 또는 테트라 치환기를 나타낼 수 있고; R₁은 수소, 알킬, 아릴, 헤테로아릴 및 할라이드로 이루어진 군으로부터 선택되고; R₂는 수소, 알킬, 아릴 및 할라이드로 이루어진 군으로부터 선택됨)을 갖는 아자 복합체를 제조하는 것을 포함하는, 아자-디벤조티오펜 화합물 또는 아자-디벤조푸란 화합물을 제조하는 방법을 개시하고 있다. US20100187984에 개시된 아자-디벤조티오펜 및 아자-디벤조푸란 화합물은 OLED에서 호스트로서 사용된다.US20100187984 is the chemical formula

The acetic acid solution of the amino-arylthiopyridine intermediate having (where one of X ₁ and X ₂ is nitrogen, the other of X ₁ and X ₂ is carbon, and Y is S or O) is treated with tBuONO to formula

(Where R ₁ and R ₂ may represent a mono, di, tri or tetra substituent; R ₁ is selected from the group consisting of hydrogen, alkyl, aryl, heteroaryl and halide; R ₂ is hydrogen, alkyl, aryl And aza complexes selected from the group consisting of halides), and methods for preparing aza-dibenzothiophene compounds or aza-dibenzofuran compounds. The aza-dibenzothiophene and aza-dibenzofuran compounds disclosed in US20100187984 are used as hosts in OLEDs.

See also WO2012090967, WO2011137072, WO2010090077, WO2009060780, WO2009060757, JP2011084531 and JP2008074939 for aza-dibenzofuranyl substituted compounds and their use in OLEDs.

None of the above references discloses aza-dibenzofuran compounds which are benzimidazo[1,2-a]benzimidazo-5-yl substituted.

Despite this development, there remains a need for an organic light emitting device comprising a novel hole transport material to provide improved efficiency, safety, manufacturability and/or spectral properties of the electroluminescent device.

Accordingly, it is an object of the present invention to provide additional materials suitable for use in OLEDs and further uses in organic electronics, in connection with the aforementioned prior art. More particularly, it should be possible to provide hole transport materials, electron/exciter blocker materials and matrix materials for use in OLEDs. The material should be particularly suitable for OLEDs comprising at least one phosphorescent emitter, in particular at least one green emitter or at least one blue emitter. In addition, the material must be suitable to provide an OLED that guarantees the OLED's excellent efficiency, good operating life and high stability against thermal stress, and low use and operating voltage.

Certain aza-dibenzofuran derivatives substituted with benzimidazo[1,2-a]benzimidazo-5-yl groups and/or benzimidazo[1,2-a]benzimidazo-2,5-ylene groups Has been found to be suitable for use in organic-electroluminescent devices. In particular, the derivative is a hole transport material or host material suitable for a phosphorescence emitter having excellent efficiency and durability.

This object was solved by the compound of formula (I).

(I)

(I)

In the above formula,

B ¹ is N or CR ⁸¹ ,

B ² is N or CR ⁸² ,

B ³ is N or CR ⁸³ ,

B ⁴ is N or CR ⁸⁴ ,

B ⁵ is N or CR ⁸⁵ ,

B ⁶ is N or CR ⁸⁶ ,

B ⁷ is N or CR ⁸⁷ ,

B ⁸ is N or CR ⁸⁸ ,

R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are independently of each other C ₁ -C ₂₅ which may be optionally substituted by H, and/or D may be interposed. Alkyl groups; A C ₆ -C ₂₄ aryl group optionally substituted by G, a C ₂ -C ₃₀ heteroaryl group optionally substituted by G; Or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ,

o is 0 or 1, p is 0 or 1, q is 0 or 1, r is 0 or 1,

A ¹ , A ² , A ³ and A ⁴ are independently of each other a C ₆ -C ₂₄ arylene group which may be optionally substituted by G, or a C ₂ -C ₃₀ heteroarylene group which may be optionally substituted by G ego;

R ¹⁶ is —NR ¹⁰ R ¹¹ , or —Si(R ¹² )(R ¹³ )(R ¹⁴ ), a C ₆ -C ₂₄ aryl group which may be optionally substituted by G; Or a C ₂ -C ₃₀ heteroaryl group which may be optionally substituted by G;

R ¹⁰ and R ¹¹ are independently of each other a C ₆ -C ₂₄ aryl group which may be optionally substituted by G; Or a C ₂ -C ₃₀ heteroaryl group which may be optionally substituted by G;

R ¹² , R ¹³ and R ¹⁴ are independently of each other a C ₁ -C ₂₅ alkyl group which may be optionally substituted by E and/or may be interrupted by D; A C ₆ -C ₂₄ aryl group which may be optionally substituted by G; Or a C ₂ -C ₃₀ heteroaryl group which may be optionally substituted by G;

D is -CO-, -COO-, -S-, -SO-, -SO ₂ -, -O-, -NR ⁶⁵ -, -SiR ⁷⁰ R ⁷¹ -, -POR ⁷² -, -CR ⁶³ =CR ⁶⁴ -Or -C≡C-,

E is -OR ⁶⁹ , -SR ⁶⁹ , -NR ⁶⁵ R ⁶⁶ , -COR ⁶⁸ , -COOR ⁶⁷ , -CONR ⁶⁵ R ⁶⁶ , -CN or F,

G is E, or a C ₁ -C ₁₈ alkyl group, C ₆ -C ₂₄ aryl group; F, a C ₆ -C ₂₄ aryl group substituted by a C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkyl, O is interposed; C ₂ -C ₃₀ heteroaryl group, or F, C ₁ -C ₁₈ alkyl or O is interposed a C ₁ a C ₂ -C ₃₀ heteroaryl group is substituted by -C ₁₈ alkyl;

R ⁶³ and R ⁶⁴ are independently of each other H, C ₆ -C ₁₈ aryl; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl; Or C ₁ -C ₁₈ alkyl interrupted by -O-;

R ⁶⁵ and R ⁶⁶ are independently of each other a C ₆ -C ₁₈ aryl group; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-; or

R ⁶⁵ and R ⁶⁶ together form a 5 or 6 membered ring,

R ⁶⁷ is a C ₆ -C ₁₈ aryl group; A C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-,

R ⁶⁸ is H; C ₆ -C ₁₈ aryl group; A C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-,

R ⁶⁹ is C ₆ -C ₁₈ aryl; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-,

R ⁷⁰ and R ⁷¹ are independently of each other a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl,

R ⁷² is a C ₁ -C ₁₈ alkyl group, C ₆ -C ₁₈ aryl group, or C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl, provided that

At least one of the substituents B ¹ , B ² , B ³ , B ⁴ , B ⁵ , B ⁶ , B ⁷ and B ⁸ represents N;

Up to ^{two of the} groups B ¹ , B ² , B ³ and B ⁴ represent N;

Up to two of the groups B ⁵ , B ⁶ , B ⁷ and B ⁸ represent N;

Additionally, provided that at least one of the substituents R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ is of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) represents a group of _r -R ¹⁶ , wherein R ¹⁶ represents a benzimidazo[1,2-a]benzimidazo-5-yl group which may be optionally substituted by G; At least one of the groups A ¹ , A ² , A ³ and A ⁴ represents a benzimidazo[1,2-a]benzimidazo-2,5-ylene group, which may be optionally substituted by G.

Certain compounds of the present invention have a LUMO-level of 2.0-2.5 eV and exhibit particularly excellent power efficiency when used as a host in combination with a phosphorescent emitter. Electroluminescent (EL) devices comprising the compounds of the present invention exhibit reduced driving voltages while maintaining excellent brightness characteristics.

The compounds of the present invention are electrophotographic photoreceptors, photoelectric converters, organic solar cells (organic photovoltaic devices), switching elements such as organic transistors, eg organic FETs and organic TFTs, organic light-emitting field effect transistors (OLEFETs), image sensors , Dye lasers and electroluminescent devices, such as for example organic light emitting diodes (OLEDs).

Accordingly, a further subject of the invention relates to an electronic device comprising the compound according to the invention. The electronic device is preferably an electroluminescent device.

The compound of formula (I) can in principle be used in any layer of the EL device, but is preferably used as a host, hole transport and electron blocking material. In particular, the compound of formula (I) is used as a host material for a blue light-emitting phosphor emitter.

Accordingly, a further subject of the invention relates to a hole transport layer comprising a compound of formula (I) according to the invention.

A further object of the invention relates to a release layer comprising a compound of formula (I) according to the invention. In this embodiment, the compound of formula (I) is preferably used as a host material in combination with a phosphorescent emitter.

The compound of formula (I) preferably has a molecular weight of less than 1500 g/mol.

A further object of the invention relates to an electron blocking layer comprising a compound of formula (I) according to the invention.

), 벤즈이미다조[1,2-a]벤즈이미다조-2-일 (

), 카르바졸릴, 디벤조푸라닐이고, 이는 비치환되거나, 또는 특히 C₆-C₁₀아릴, 또는 C₁-C₄알킬에 의해 치환된 C₆-C₁₀아릴; 또는 C₂-C₁₄헤테로아릴에 의해 치환될 수 있다.D is preferably -CO-, -COO-, -S-, -SO-, -SO ₂ -, -O-, -NR ⁶⁵ -, where R ⁶⁵ is C ₁ -C ₁₈ alkyl, such as methyl, Ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, or sec-butyl, or C ₆ -C ₁₄ aryl, such as phenyl, tolyl, naphthyl or biphenylyl, or C ₂ -C ₃₀ heteroaryl , For example, benzimidazo[1,2-a]benzimidazo-5-yl (

), Benzimidazo [1,2-a] Benzimidazo-2-yl (

), carbazolyl, dibenzofuranyl, which is unsubstituted or especially C ₆ -C ₁₀ aryl, or C ₆ -C ₁₀ aryl substituted by C ₁ -C ₄ alkyl; Or C ₂ -C ₁₄ heteroaryl.

E is preferably -OR ⁶⁹ ; -SR ⁶⁹ ; -NR ⁶⁵ R ⁶⁵ ; -COR ⁶⁸ ; -COOR ⁶⁷ ; -CONR ⁶⁵ R ⁶⁵ ; Or -CN; Wherein R ⁶⁵ , R ⁶⁷ , R ⁶⁸ and R ⁶⁹ are independently of _one another C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl , Or 2-ethyl-hexyl, or C ₆ -C ₁₄ aryl, such as phenyl, tolyl, naphthyl or biphenylyl.

Among the compounds of formula (I), the following formula

Preferred is a compound of R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁵ , R ⁸⁶ and R ⁸⁷ have the (preferred) meanings given above and below, respectively.

In a preferred embodiment, the invention relates to compounds of the formula

In the above formula, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁵ , R ⁸⁶ and R ⁸⁷ are as defined above.

Preferred are compounds of formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ii), (Ij), (Il) and (In). Particularly preferred are compounds of formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ij) and (In).

R ^16' (R ¹⁶ ) may be a C ₆ -C ₂₄ aryl group optionally substituted by G, or a C ₂ -C ₃₀ heteroaryl group optionally substituted by G.

C ₆ -C ₂₄ aryl groups which may be optionally substituted by G are typically phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl or 2-naphthyl, biphenylyl, terphenylyl , Pyrenyl, 2- or 9-fluorenyl, phenanthryl or anthryl, which may be unsubstituted or substituted.

The C ₂ -C ₃₀ heteroaryl group R ^16' (R ¹⁶ ), which may be optionally substituted by G, represents a ring or fused ring system having 5 to 7 ring atoms, wherein nitrogen, oxygen or sulfur is a possible hetero atom , And a heterocyclic group having 5 to 30 atoms, typically having at least 6 conjugated π-electrons, such as 9H-pyrido[2,3-b]indolyl, benzofuro[2,3-b]pyri Dill, benzothiopheno[2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3 -c]pyridyl, furo[3,2-b:4,5-b']dipyridyl, pyrrolo[3,2-b:4,5-b']dipyridyl, thieno[3, 2-b:4,5-b']dipyridyl, thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, Dibenzofuranyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indole Reel, indazolyl, purinyl, quinolinyl, quinolyl, isokinolyl, phthalazinyl, naphthyridinyl, kinoxalinyl, kinazolinyl, cynolinyl, pteridinyl, carbolinyl, benzotriazolyl , Benzoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, benzimidazo[1,2-a]benz Imidazo-5-yl, benzimidazo[1,2-a]benzimidazo-2-yl, carbazolyl or phenoxazinyl, which may be unsubstituted or substituted.

C ₆ -C ₂₄ aryl and C ₂ -C ₃₀ heteroaryl groups may be substituted by G.

G has the same preferred definition as E, or C ₁ -C ₁₈ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, hexyl, octyl or 2-ethyl -Hexyl, or C ₁ -C ₁₈ perfluoroalkyl, for example -CF ₃ .

), 벤즈이미다조[1,2-a]벤즈이미다조-2-일 (

), 카르바졸릴, 디벤조푸라닐 및 디벤조티오페닐이고, 이는 비치환되거나, 또는 특히 C₆-C₁₀아릴, 또는 C₁-C₄알킬에 의해 치환된 C₆-C₁₀아릴; 또는 C₂-C₁₄헤테로아릴에 의해 치환될 수 있다.Preferred C ₂ -C ₃₀ heteroaryl groups are pyridyl, triazinyl, pyrimidinyl, especially 9H-pyrido[2,3-b]indolyl, benzofuro[2,3-b]pyridyl, benzothiopheno [2,3-b]pyridyl, 9H-pyrido[2,3-c]indolyl, benzofuro[2,3-c]pyridyl, benzothiopheno[2,3-c]pyridyl, Furo[3,2-b:4,5-b']dipyridyl, pyrrolo[3,2-b:4,5-b']dipyridyl, thieno[3,2-b:4, 5-b']dipyridyl, benzimidazo[1,2-a]benzimidazo-5-yl (

), Benzimidazo [1,2-a] Benzimidazo-2-yl (

), carbazolyl, dibenzofuranyl and dibenzothiophenyl, which are unsubstituted or in particular C ₆ -C ₁₀ aryl, or C ₆ -C ₁₀ aryl substituted by C ₁ -C ₄ alkyl; Or C ₂ -C ₁₄ heteroaryl.

의 기이거나, 또는 기 A¹, A², A³ 및 A⁴ 중 적어도 1개가 화학식

의 기를 나타내는 경우에 R¹⁶은 R^16'의 의미를 갖는다.R ¹⁶ is a chemical formula

Or is at least one of the groups A ¹ , A ² , A ³ and A ⁴

In the case of representing a group of R ¹⁶ has the meaning of R ^16' .

R ^16' is preferably H, or the formula -Si(R ¹² )(R ¹³ )(R ¹⁴ ), in particular

It is a flag.

R ¹² , R ¹³ and R ¹⁴ are, independently of each other, a phenyl group which may be optionally substituted by one or more C ₁ -C ₁₈ alkyl groups;

R ²¹ and R ^21' are each independently H, a phenyl group or a C ₁ -C ₁₈ alkyl group;

R ²² and R ²³ are each independently H, or a formula

의 기이고;

Is a group of;

X is O, S or NR ²⁴ ,

R ²⁴ is a C ₆ -C ₂₄ aryl group or C ₂ -C ₃₀ heteroaryl group, which may be optionally substituted by G, where G is as defined above;

R ⁸⁹ is H, chemical formula

It is a flag.

A ¹ , A ² , A ³ and A ⁴ are independently of each other a C ₆ -C ₂₄ arylene group which may be optionally substituted by G, or a C ₂ -C ₃₀ heteroarylene group which may be optionally substituted by G to be. C ₆ -C ₂₄ arylene groups A ¹ , A ² , A ³ and A ⁴ which may be optionally substituted by G are typically phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1 -Naphthylene or 2-naphthylene, biphenylylene, terphenylylene, pyrenylene, 2- or 9-fluorenylene, phenanthrene or anthylene, which may be unsubstituted or substituted.

), 벤조티오페노[2,3-b]피리딜렌 (

), 피리도[2,3-b]인돌릴렌 (

), 벤조푸로[2,3-c]피리딜렌 (

), 벤조티오페노[2,3-c]피리딜렌 (

), 피리도[2,3-c]인돌릴렌 (

), 푸로[3,2-b:4,5-b']디피리딜렌 (

), 티에노[3,2-b:4,5-b']디피리딜렌 (

), 피롤로[3,2-b:4,5-b']디피리딜렌 (

), 티에닐렌, 벤조티오페닐렌, 티안트레닐렌, 푸릴렌, 푸르푸릴렌, 2H-피라닐렌, 벤조푸라닐렌, 이소벤조푸라닐렌, 디벤조푸라닐렌 (

), 디벤조티오페닐렌 (

), 페녹시티에닐렌, 피롤릴렌, 이미다졸릴렌, 피라졸릴렌, 피리딜렌, 비피리딜렌, 트리아지닐렌, 피리미디닐렌, 피라지닐렌, 피리다지닐렌, 인돌리지닐렌, 이소인돌릴렌, 인돌릴렌, 인다졸릴렌, 퓨리닐렌, 퀴놀리지닐렌, 키놀릴렌, 이소키놀릴렌, 프탈라지닐렌, 나프티리디닐렌, 키녹살리닐렌, 키나졸리닐렌, 신놀리닐렌, 프테리디닐렌, 카르볼리닐렌, 벤조트리아졸릴렌, 벤족사졸릴렌, 페난트리디닐렌, 아크리디닐렌, 피리미디닐렌, 페난트롤리닐렌, 페나지닐렌, 이소티아졸릴렌, 페노티아지닐렌, 이속사졸릴렌, 푸라자닐렌, 카르바졸릴렌 (

), 벤즈이미다조[1,2-a]벤즈이미다조-2,5-일렌 (

) 또는 페녹사지닐렌이고, 이는 비치환되거나 또는 치환될 수 있다.C ₂ -C ₃₀ heteroarylene groups A ¹ , A ² , A ³ and A ⁴ which may be optionally substituted by G represent a ring or fused ring system having 5 to 7 ring atoms, wherein nitrogen, oxygen Or sulfur is a possible hetero atom, typically a heterocyclic group having 5 to 30 atoms with at least 6 conjugated π-electrons, such as benzofuro[2,3-b]pyridylene (

), benzothiopheno[2,3-b]pyridylene (

), pyrido[2,3-b]indolylene (

), benzofuro[2,3-c]pyridylene (

), benzothiopheno[2,3-c]pyridylene (

), pyrido[2,3-c]indolelene (

), furo[3,2-b:4,5-b']dipyridylene (

), thieno[3,2-b:4,5-b']dipyridylene (

), pyrrolo[3,2-b:4,5-b']dipyridylene (

), thienylene, benzothiophenylene, thiantrenylene, furylene, furfurylene, 2H-pyranylene, benzofuranylene, isobenzofuranylene, dibenzofuranylene (

), dibenzothiophenylene (

), phenoxyethylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridazinylene, indolizinylene, isoin Dolylene, Indolylene, Indazolylene, Purinylene, Quinolizinylene, Kinolelyne, Isoquinolelene, Phthalazinylene, Naphthyridinylene, Kinoxalinylene, Kinazolinylene, Sinnolinylene, Pteriri Dinilene, carbolinylene, benzotriazolylene, benzoxazolylene, phenanthridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, isothiazolylene, phenothiazinylene, isoxa Zolylene, furazanilen, carbazolylene (

), Benzimidazo[1,2-a]benzimidazo-2,5-ylene (

) Or phenoxazinylene, which may be unsubstituted or substituted.

Preferred C ₆ -C ₂₄ arylene groups are 1,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrene, This is unsubstituted or, especially C ₆ -C ₁₀ aryl, C ₁ -C of C ₆ -C ₁₀ aryl which is substituted by _4-alkyl; Or C ₂ -C ₁₄ heteroaryl.

Preferred C ₂ -C ₃₀ heteroarylene groups are pyridylene, triazinylene, pyrimidinylene, especially benzofuro[2,3-b]pyridylene, benzothiopheno[2,3-b]pyridylene, pyrido [2,3-b]indolylene, benzofuro[2,3-c]pyridylene, benzothiopheno[2,3-c]pyridylene, pyrido[2,3-c]indolelene, furo[ 3,2-b:4,5-b']dipyridylene, thieno[3,2-b:4,5-b']dipyridylene, pyrrolo[3,2-b:4,5- b']dipyridylene, dibenzofuranylene, dibenzothiophenylene, carbazolylene and benzimidazo[1,2-a]benzimidazo-2,5-ylene, which are unsubstituted or in particular C ₆ -C ₁₀ aryl, C ₁ -C of C ₆ -C ₁₀ aryl which is substituted by _4-alkyl; Or C ₂ -C ₁₄ heteroaryl.

Benzimidazo[1,2-a]benzimidazo-5-yl, benzimidazo[1,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are C ₂ -C ₁₄ It is an example of a heteroaryl group. Phenyl, 1-naphthyl and 2-naphthyl are examples of C ₆ -C ₁₀ aryl groups.

C ₆ -C ₂₄ arylene and C ₂ -C ₃₀ heteroarylene groups may be substituted by G.

A ¹ , A ² , A ³ and A ⁴ are preferably chemical formulas

And wherein R ⁸⁹ and X are as defined below. X is preferably O.

The aza-dibenzofuran derivatives of the present invention are those in which at least one benzimidazo[1,2-a]benzimidazo-5-yl group and/or at least one benzimidazo[1,2-a]benzimid It is characterized by being substituted with a dazo-2,5-ylene group.

의 기이고/거나; 치환기 R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷ 및 R⁸⁸ 중 적어도 1개가 화학식 -(A¹)_o-(A²)_p-(A³)_q-(A⁴)_r-R^16'의 기이고, 여기서 기 A¹, A², A³ 및 A⁴ 중 적어도 1개는 화학식

의 기를 나타내는 것을 특징으로 한다.In particular, the aza-dibenzofuran derivative of the present invention is a substituent R ⁸¹ , R ⁸² , R ⁸³ , At least one of R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ , Where R ¹⁶ is the chemical formula

And/or Substituents R ⁸¹ , R ⁸² , R ⁸³ , At least one of R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' , Wherein at least one of the groups A ¹ , A ² , A ³ and A ⁴ is a chemical formula

It is characterized by indicating the flag.

In a preferred embodiment, the invention provides formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ig), (Ih), (Ii), (Ij), ( Ik), (Il), (Im), (In) and (Io).

For compounds of formula (Ia)

R ⁸³ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁷ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸³ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Ib)

R ⁸² is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁷ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸² is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Ic)

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁷ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Id)

R ⁸¹ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸¹ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Ie)

R ⁸³ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁷ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸³ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (If)

R ⁸³ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸³ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Ig)

R ⁸² is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸² is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Ih)

R ⁸¹ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁷ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸¹ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Ii)

R ⁸³ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸³ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Ij)

R ⁸³ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸³ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Ik)

R ⁸¹ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸¹ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Il)

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁷ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (Im)

R ⁸³ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁵ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸³ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁵ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

For compounds of formula (In)

R ⁸³ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁷ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸³ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

o is 0 or 1, p is 0 or 1, q is 0 or 1, and r is 0 or 1;

For compounds of formula (Io)

R ⁸² is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

R ⁸⁶ is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ; or

R ⁸² is H or a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' ;

R ⁸⁶ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ ;

A ¹ , A ² , A ³ and A ⁴ are independently of each other

Is a group of;

의 기이거나, 또는 기 A¹, A², A³ 및 A⁴ 중 적어도 1개가 화학식

의 기를 나타내는 경우에 R¹⁶은 R^16'의 의미를 갖고;R ¹⁶ is a chemical formula

Or is at least one of the groups A ¹ , A ² , A ³ and A ⁴

R ¹⁶ in the case of representing a group has the meaning of R ^16' ;

,R ^16' is H, or the formula -Si(R ¹² )(R ¹³ )(R ¹⁴ ),

,

Is a group of;

R ¹² , R ¹³ and R ¹⁴ are each independently a phenyl group which may be optionally substituted by one or more alkyl groups, in particular C ₁ -C ₁₈ alkyl groups;

R ²¹ and R ^21' are each independently H, a phenyl group or a C ₁ -C ₁₈ alkyl group;

R ²² and R ²³ are each independently H, or a formula

의 기이고;

Is a group of;

X is O, S or NR ²⁴ ,

R ²⁴ is a C ₆ -C ₂₄ aryl group or C ₂ -C ₃₀ heteroaryl group, which may be optionally substituted by G, where G is as defined above;

R ⁸⁹ is H, chemical formula

It is a flag.

More preferably, A ¹ , A ² , A ³ and A ⁴ are independently of each other

Is a group of;

의 기이거나; 또는 기 A¹, A², A³ 및 A⁴ 중 적어도 1개가 화학식

의 기를 나타내는 경우에 R¹⁶은 R^16'의 의미를 갖고;R ¹⁶ is a chemical formula

Is a group of; Or at least one of the groups A ¹ , A ² , A ³ and A ⁴ is a chemical formula

R ¹⁶ in the case of representing a group has the meaning of R ^16' ;

R ^16' is H, or a chemical formula

또는Is a group of; R ⁸⁹ is H, chemical formula

or

의 기이고, 여기서, X는 O, S 또는 NR²⁴이고, 여기서 R²⁴는

이다.

Is a group, wherein X is O, S or NR ²⁴ , where R ²⁴ is

to be.

이다. X는 바람직하게는 O이다.R ²⁴ is preferably

to be. X is preferably O.

The group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ is preferably a formula

It is a flag.

The group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ^16' is preferably H, or formulas (XIIa), (XIIb) as defined above , (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), (XIIk), ((XIIl)), (XIIm), (XIIn) , (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), ( Groups of XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg); Or chemical formula

It is a flag.

In a preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸³ is as defined above XIIk), (XIIl), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw) , (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) Group of compounds of formula (Ia); or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁷ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The group relates to a compound of formula (Ia).

In the above embodiment, R ⁸³ is as defined above (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb) ), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compound of formula (Ia) which is the group of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁷ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of formula (Ia), which are groups of) are more preferred.

In a preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸² are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) Group of compounds of formula (Ib); or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁷ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸² is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The group relates to a compound of formula (Ib).

In the above embodiment, formula (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), wherein R ⁸² is as defined above, (XIIn), (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb) ), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of formula (Ib) which are groups of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁷ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸² is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of the formula (Ib), which are groups of) are more preferred.

In a preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁵ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The compound of formula (Ic); or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁷ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) groups;

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The group relates to a compound of formula (Ic).

In the above embodiment, R ⁸⁵ is as defined above (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb) ), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compound of formula (Ic) which is the group of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁷ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of formula (Ic), which are groups of) are more preferred.

In a preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸¹ is as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) Groups of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg); Or as defined above (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr) , (XIVs), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), ( (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq) , (XVr), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or ( Compound of formula (Id), which is a group of XVId); or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁵ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) groups;

R ⁸¹ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) It relates to the compound of formula (Id) which is a group.

In the above embodiment, R ⁸¹ is as defined above (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb) ), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compound of formula (Id) which is the group of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁵ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸¹ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of formula (Id), which are groups of) are more preferred.

In a preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸³ is as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The group is a compound of formula (Ie); or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁷ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The group relates to a compound of formula (Ie).

In the above embodiment, R ⁸³ is as defined above (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb) ), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of formula (Ie) which are groups of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁷ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of the formula (Ie), which are groups of) are more preferred.

In a preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸³ is as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) Compounds of the formula (If) attributable to; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁵ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) It relates to the compound of the formula (If) attributable.

In the above embodiment, R ⁸³ is as defined above (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb) ), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compound of formula (If), which is a group of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁵ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) The compound of the formula (If), which is a group of ), is more preferable.

In a preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸³ is as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The compound of formula (Ij); or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁵ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The group relates to a compound of formula (Ij).

In the above embodiment, R ⁸³ is as defined above (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb) ), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compound of formula (Ij) which is the group of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁵ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of the formula (Ij), which are groups of) are more preferred.

In a preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁵ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) A compound of formula (Il) attributable to; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁷ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸⁵ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The group relates to a compound of formula (Il).

In a preferred embodiment, the invention provides that R ⁸³ is of the formula (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi) , (XIIj), (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu) , (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group ego,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) Group of compounds of formula (In); or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj), wherein R ⁸⁷ are as defined above XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv), ( XIIw), a group of (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg),

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIh), (XIIi), (XIIj) as defined above , (XIIk), ((XIIl)), (XIIm), (XIIn), (XIIo), (XIIp), (XIIq), (XIIr), (XIIs), (XIIt), (XIIu), (XIIv) A group of (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or the above definition Formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg), (XIVh), (XIVo), (XIVp), (XIVq), (XIVr), (XIVs) as ), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVy), (XIVz), (XVa), (XVb), (XVc), (XVd), (XVe), (XVf), (XVg), (XVh), (XVi), (XVj), (XVk), (XVl), (XVm), (XVn), (XVo), (XVp), (XVq), (XVr) ), (XVs), (XVt), (XVu), (XVv), (XVw), (XVx), (XVy), (XVz), (XVIa), (XVIb), (XVIc) or (XVId) The group relates to a compound of formula (In).

In the above embodiment, R ⁸³ is as defined above (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb) ), (XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compound of formula (In) which is the group of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁷ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of the formula (In), which are groups of) are more preferred.

Examples of preferred compounds are compounds A-1 to A-65, B-1 to B-8, C-1 to C-65, D-1 to D-8, E-1 to E shown in claim 9 -65, F-1 to F-65 and G-1.

In a particularly preferred embodiment, the invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), wherein R ⁸³ is as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compound of formula (Ia) which is the group of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁷ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compound of formula (Ia) which is the group of; For example relates to compound (A-4).

In another particularly preferred embodiment, the present invention

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), wherein R ⁸³ is as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

R ⁸⁷ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of formula (Ie) which are groups of; or

Formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn), (R ⁸⁷ ) as defined above XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), (XIIIc) , (XIIId), (XIIIe), (XIIIf) or (XIIIg) group,

에 관한 것이다.R ⁸³ is H, formulas (XIIa), (XIIb), (XIIc), (XIId), (XIIe), (XIIf), (XIIg), (XIIj), (XIIk), (XIIn) as defined above , (XIIo), (XIIq), (XIIs), (XIIt), (XIIu), (XIIv), (XIIw), (XIIx), (XIIy), (XIIz), (XIIIa), (XIIIb), ( A group of XIIIc), (XIIId), (XIIIe), (XIIIf) or (XIIIg), or formulas (XIVb), (XIVc), (XIVd), (XIVe), (XIVf), (XIVg) as defined above ), (XIVo), (XIVp), (XIVq), (XIVr), (XIVt), (XIVu), (XIVv), (XIVw), (XIVx), (XIVz), (XVa), (XVb), (XVc), (XVk), (XVl), (XVo), (XVp), (XVs), (XVw), (XVx), (XVy), (XVIa), (XVIb), (XVIc), or (XVId) Compounds of formula (Ie) which are groups of; For example compounds

It is about.

Compounds such as (E-57) can be advantageously used as host and/or hole transport materials.

과 같은 화합물은 전자 수송 물질로서 특히 적합하다.For example

Such compounds are particularly suitable as electron transport materials.

Halogens are fluorine, chlorine, bromine and iodine.

C ₁ -C ₂₅ alkyl (C ₁ -C ₁₈ alkyl) is typically linear, or branched where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, 1 ,1,3,3-tetramethylpentyl, n-hexyl, 1-methylhexyl, 1,1,3,3,5,5-hexamethylhexyl, n-heptyl, isoheptyl, 1,1,3,3 -Tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodecyl, tridecyl , Tetradecyl, pentadecyl, hexadecyl, heptadecyl or octadecyl. C ₁ -C ₈ alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2 ,2-dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl. C ₁ -C ₄ alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec.-butyl, isobutyl, tert.-butyl.

C ₁ -C ₂₅ alkoxy groups (C ₁ -C ₁₈ alkoxy groups) are straight-chain or branched alkoxy groups, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-part Methoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, penta Decyloxy, hexadecyloxy, heptadecyloxy and octadecyloxy. Examples of C ₁ -C ₈ alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, 2 -Pentyloxy, 3-pentyloxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexyl Siloxy, preferably C ₁ -C ₄ alkoxy, such as typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.-butoxy, isobutoxy, tert.-butoxy to be.

C ₁ -C ₁₈ perfluoroalkyl, in particular C ₁ -C ₄ perfluoroalkyl, is a branched or unbranched radical, for example -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF(CF ₃ ) ₂ , -(CF ₂ ) ₃ CF ₃ and -C(CF ₃ ) ₃ .

The term "cycloalkyl group" is typically C ₄ -C ₁₈ cycloalkyl, especially C ₅ -C ₁₂ cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclo Dodecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, which may be unsubstituted or substituted.

C ₆ -C ₂₄ aryl which may be optionally substituted (C ₆ -C ₁₈ aryl) is typically phenyl, 4-methylphenyl, 4-methoxyphenyl, naphthyl, especially 1-naphthyl or 2-naphthyl, biphenyl Reel, terphenylyl, pyrenyl, 2- or 9-fluorenyl, phenanthryl or anthryl, which may be unsubstituted or substituted. Phenyl, 1-naphthyl and 2-naphthyl are examples of C ₆ -C ₁₀ aryl groups.

C ₂ -C ₃₀ heteroaryl refers to a ring or condensed ring system having 5 to 7 ring atoms, wherein nitrogen, oxygen or sulfur is a possible hetero atom, typically 5 to 30 having at least 6 conjugated π-electrons Heterocyclic groups having atoms such as thienyl, benzothiophenyl, dibenzothiophenyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxy Citienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, fury Neil, quinolinyl, quinolyl, isokinolyl, phthalazinyl, naphthyridinyl, kinoxalinyl, kinazolinyl, cynolinyl, pteridinyl, carbazolyl, carbolinyl, benzotriazolyl, ben Zoxazolyl, phenanthridinyl, acridinyl, pyrimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, 4-imidazo[1,2-a]benzimi Dazoyl, 5-benzimidazo[1,2-a]benzimidazoyl, carbazolyl or phenoxazinyl, which may be unsubstituted or substituted. Benzimidazo[1,2-a]benzimidazo-5-yl, benzimidazo[1,2-a]benzimidazo-2-yl, carbazolyl and dibenzofuranyl are C ₂ -C ₁₄ It is an example of a heteroaryl group.

C ₆ -C ₂₄ arylene groups which may be optionally substituted by G are typically phenylene, 4-methylphenylene, 4-methoxyphenylene, naphthylene, especially 1-naphthylene or 2-naphthylene, biphenylylene , Terphenylylene, pyrenylene, 2- or 9-fluorenylene, phenanthrene or anthylene, which may be unsubstituted or substituted. Preferred C ₆ -C ₂₄ arylene groups are 1,3-phenylene, 3,3'-biphenylylene, 3,3'-m-terphenylene, 2- or 9-fluorenylene, phenanthrene, It can be unsubstituted or substituted.

)이고, 이는 비치환되거나, 또는 특히 C₆-C₁₀아릴, C₁-C₄알킬에 의해 치환된 C₆-C₁₀아릴; 또는 C₂-C₁₄헤테로아릴에 의해 치환될 수 있다.A C ₂ -C ₃₀ heteroarylene group optionally substituted by G represents a ring or condensed ring system having 5 to 7 ring atoms, wherein nitrogen, oxygen or sulfur is a possible hetero atom, typically at least 6 conjugates Heterocyclic groups having 5 to 30 atoms with π-electrons, such as thienylene, benzothiophenylene, dibenzothiophenylene, thiantrenylene, furylene, furfurylene, 2H-pyranylene, benzofura Nylene, isobenzofuranylene, dibenzofuranylene, phenoxythienylene, pyrrolylene, imidazolylene, pyrazolylene, pyridylene, bipyridylene, triazinylene, pyrimidinylene, pyrazinylene, pyridane Genylene, indolizinylene, isoindolelene, indolylene, indazolylene, purinylene, quinolizinylene, kinoylene, isokinolelene, phthalazinylene, naphthyridinylene, kinoxalinylene, Kinazolinylene, cynolinylene, pteridinylene, carbolinylene, benzotriazolylene, benzoxazolylene, phenanthridinylene, acridinylene, pyrimidinylene, phenanthrolinylene, phenazinylene, isothia Zolylene, phenothiazinylene, isoxazolylene, furazanilen, carbazolylene, benzimidazo[1,2-a]benzimidazo-2,5-ylene or phenoxazinylene, which is a beach May be substituted or substituted. Preferred C ₂ -C ₃₀ heteroarylene groups are pyridylene, triazinylene, pyrimidinylene, carbazolylene, dibenzofuranylene and benzimidazo[1,2-a]benzimidazo-2,5-ylene (

), And which is unsubstituted or, especially, or C ₆ -C ₁₀ aryl, C ₁ -C ₄ alkyl, C ₆ -C ₁₀ aryl which is substituted by; Or C ₂ -C ₁₄ heteroaryl.

Possible substituents for the aforementioned groups are C ₁ -C ₈ alkyl, hydroxyl groups, mercapto groups, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, halogen, halo-C ₁ -C ₈ alkyl or cyan It is Nogi.

C ₆ -C ₂₄ aryl (C ₆ -C ₁₈ aryl) and C ₂ -C ₃₀ heteroaryl groups are preferably substituted by one or more C ₁ -C ₈ alkyl groups.

When a substituent is present more than once in a group, it can be different in each case.

The phrase "substituted by G" means that there may be one or more, especially one to three substituents G.

As described above, the above-mentioned groups may be substituted by E and/or D may be interposed if desired. Intervening as well as if the group contains at least two carbon atoms bonded to each other by a single bond; C ₆ -C ₁₈ aryl is not interposed; The intervening arylalkyl contains unit D in the alkyl moiety. C ₁ -C ₁₈ alkyl substituted by one or more E and/or interrupted by one or more units D is, for example, (CH ₂ CH ₂ O) _1-9 -R ^x (where R ^x is H or C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkanoyl (eg, CO-CH(C ₂ H ₅ )C ₄ H ₉ )), CH ₂ -CH(OR ^y' )-CH ₂ -OR ^y (where R ^y is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, C ₇ -C ₁₅ phenylalkyl, R ^y′ encompasses the same definition as R ^y or is H);

C ₁ -C ₈ alkylene-COO-R ^z , for example CH ₂ COOR ^z , CH(CH ₃ )COOR ^z , C(CH ₃ ) ₂ COOR ^z (where R ^z is H, C ₁ -C ₁₈ Alkyl, (CH ₂ CH ₂ O) _1-9 -R ^x , R ^x encompasses the definitions indicated above);

CH ₂ CH ₂ -O-CO-CH=CH ₂ ; CH ₂ CH(OH)CH ₂ -O-CO-C(CH ₃ )=CH ₂ .

의 합성은, 예를 들어 문헌 [Achour, Reddouane; Zniber, Rachid, Bulletin des Societes Chimiques Belges 96 (1987) 787-92]에 기재되어 있다.

The synthesis of, for example, Achour, Reddouane; Zniber, Rachid, Bulletin des Societes Chimiques Belges 96 (1987) 787-92.

의 적합한 기본 골격은 상업적으로 입수가능하거나 (특히 X가 S, O, NH인 경우에), 또는 통상의 기술자에게 공지된 방법에 의해 수득될 수 있다. WO2010079051 및 EP1885818을 참조한다.Chemical formula

Suitable basic frameworks for are commercially available (especially when X is S, O, NH), or can be obtained by methods known to those skilled in the art. See WO2010079051 and EP1885818.

Halogenation can be performed by methods known to those skilled in the art. 3 and 6 positions (dibromination) of the basic backbone of the formula (II) 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole), or 3 or 6 positions (monobromination Bromine or iodination in) is preferred.

The optionally substituted dibenzofuran, dibenzothiophene and carbazole are in glacial acetic acid or chloroform at 2,8 positions (dibenzofuran and dibenzothiophene) or 3,6 positions (carbazole) using bromine or NBS. Can be dibrominated. For example, bromination with Br ₂ can be carried out in glacial acetic acid or chloroform at low temperatures, eg 0°C. A suitable method is, for example, X=NPh. Park, JR Buck, CJ Rizzo, Tetrahedron, 54 (1998) 12707-12714, and when X=S, see W. Yang et al., J. Mater. Chem. 13 (2003) 1351. In addition, 3,6-dibromocarbazole, 3,6-dibromo-9-phenylcarbazole, 2,8-dibromodibenzothiophene, 2,8-dibromodibenzofuran, 2-bro Mocarbazole, 3-bromodibenzothiophene, 3-bromodibenzofuran, 3-bromocarbazole, 2-bromodibenzothiophene and 2-bromodibenzofuran are commercially available.

Monobromination at the 4 position of dibenzofuran (and similarly for dibenzothiophene) is described, for example, in J. Am. Chem. Soc. 1984, 106, 7150. Dibenzofuran (dibenzothiophene) can be monobrominated at the 3 position by procedures known to those skilled in the art, including nitration, reduction and subsequent Sandmeyer reactions.

Monobromination at position 2 of dibenzofuran or dibenzothiophene and monobromination at position 3 of carbazole are similar to dibromination except adding only one equivalent of bromine or NBS. Is executed.

Alternatively, it is also possible to use iodinated dibenzofuran, dibenzothiophene and carbazole. Manufacturing is especially described in Tetrahedron. Lett. 47 (2006) 6957-6960, Eur. J. Inorg. Chem. 24 (2005) 4976-4984, J. Heterocyclic Chem. 39 (2002) 933-941, J. Am. Chem. Soc. 124 (2002) 11900-11907, J. Heterocyclic Chem, 38 (2001) 77-87.

For nucleophilic substitution, Cl- or F-substituted dibenzofuran, dibenzothiophene and carbazole are needed. Chlorination is specifically described in J. Heterocyclic Chemistry, 34 (1997) 891-900, Org. Lett., 6 (2004) 3501-3504; J. Chem. Soc. [Section] C: Organic, 16 (1971) 2775-7, Tetrahedron Lett. 25 (1984) 5363-6, J. Org. Chem. 69 (2004) 8177-8182. Fluorination is described in J. Org. Chem. 63 (1998) 878-880 and J. Chem. Soc., Perkin Trans. 2, 5 (2002) 953-957.

의 도입은 염기의 존재 하에 수행된다. 적합한 염기는 통상의 기술자에게 공지되어 있으며, 바람직하게는 알칼리 금속 및 알칼리 토금속 히드록시드, 예컨대 NaOH, KOH, Ca(OH)₂, 알칼리 금속 히드라이드, 예컨대 NaH, KH, 알칼리 금속 아미드, 예컨대 NaNH₂, 알칼리 금속 또는 알칼리 토금속 카르보네이트, 예컨대 K₂CO₃ 또는 Cs₂CO₃, 및 알칼리 금속 알콕시드, 예컨대 NaOMe, NaOEt로 이루어진 군으로부터 선택된다. 또한, 상기 언급된 염기의 혼합물이 적합하다. NaOH, KOH, NaH 또는 K₂CO₃이 특히 바람직하다.group

The introduction of is carried out in the presence of a base. Suitable bases are known to the skilled person and are preferably alkali metal and alkaline earth metal hydroxides such as NaOH, KOH, Ca(OH) ₂ , alkali metal hydrides such as NaH, KH, alkali metal amides such as NaNH ₂ , alkali metal or alkaline earth metal carbonates, such as K ₂ CO ₃ or Cs ₂ CO ₃ , and alkali metal alkoxides, such as NaOMe, NaOEt. Also suitable are mixtures of the bases mentioned above. NaOH, KOH, NaH or K ₂ CO ₃ are particularly preferred.

의 할로겐화 화합물에 대한

의 구리-촉매화 커플링 (울만(Ullmann) 반응)에 의해 수행될 수 있다.Heteroarylization is, for example, a formula

For halogenated compounds

Copper-catalyzed coupling (Ullmann reaction).

N-arylation is described, for example, in H. Gilman and D. A. Shirley, J. Am. Chem. Soc. 66 (1944) 888; D. Li et al., Dyes and Pigments 49 (2001) 181-186, and Eur. J. Org. Chem. (2007) 2147-2151. The reaction can be carried out in a solvent or melt. Suitable solvents are, for example (polar) aprotic solvents, such as dimethyl sulfoxide, dimethylformamide, NMP, tridecane or alcohol.

의 합성은 WO2010079051에 기재되어 있다. 2-브로모-8-아이오도-디벤조푸란

의 합성은 EP1885818에 기재되어 있다.9-(8-bromodibenzofuran-2-yl)carbazole

The synthesis of is described in WO2010079051. 2-bromo-8-iodo-dibenzofuran

The synthesis of is described in EP1885818.

의 화합물에 대한 가능한 합성 경로는 하기 반응식에 나타내었다:Chemical formula

The possible synthetic routes for the compounds of are shown in the following scheme:

See Angew. Chem. Int. Ed. 46 (2007) 1627-1629 and Synthesis 20 (2009) 3493.

Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups can be easily prepared by increasing the number of pathways. For an overview of synthetic routes, see, eg, Angew. Chem. Int. Ed. 48 (2009) 9240-9261.

와 반응시킴으로써 수득될 수 있고 (문헌 [Prasad Appukkuttan et al., Synlett 8 (2003) 1204] 참조), 여기서 Y¹은 각 경우에 독립적으로 C₁-C₁₈알킬 기이고, Y²는 각 경우에 독립적으로 C₂-C₁₀알킬렌 기, 예컨대 -CY³Y⁴-CY⁵Y⁶- 또는 -CY⁷Y⁸-CY⁹Y¹⁰-CY¹¹Y¹²-이고, 여기서 Y³, Y⁴, Y⁵, Y⁶, Y⁷, Y⁸, Y⁹, Y¹⁰, Y¹¹ 및 Y¹²는 서로 독립적으로 수소 또는 C₁-C₁₈알킬 기, 특히 -C(CH₃)₂C(CH₃)₂-, -C(CH₃)₂CH₂C(CH₃)₂- 또는 -CH₂C(CH₃)₂CH₂-이고, Y¹³ 및 Y¹⁴는 서로 독립적으로 수소 또는 C₁-C₁₈알킬 기이다.Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups by one common route are catalysts such as dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene in a solvent such as For example [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complexes (Pd(Cl) ₂ (dppf)), and halogenated di in the presence of bases such as for example potassium acetate Benzofuran, dibenzothiophene and carbazole

It can be obtained by reacting with (see Prasad Appukkuttan et al., Synlett 8 (2003) 1204), wherein Y ¹ is independently a C ₁ -C ₁₈ alkyl group in each case, and Y ² is in each case. Independently a C ₂ -C ₁₀ alkylene group, such as -CY ³ Y ⁴ -CY ⁵ Y ⁶ -or -CY ⁷ Y ⁸ -CY ⁹ Y ¹⁰ -CY ¹¹ Y ¹² -, where Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ , Y ⁸ , Y ⁹ , Y ¹⁰ , Y ¹¹ and Y ¹² are independently of each other hydrogen or a C ₁ -C ₁₈ alkyl group, in particular -C(CH ₃ ) ₂ C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ CH ₂ C(CH ₃ ) ₂ -or -CH ₂ C(CH ₃ ) ₂ CH ₂ -, Y ¹³ and Y ¹⁴ are independently of each other hydrogen or C ₁ -C ₁₈ alkyl It is Ki.

와 반응시킴으로써 제조될 수 있다 (문헌 [Synthesis (2000) 442-446] 참조).Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups also include halogenated dibenzofuran, dibenzothiophene and carbazole with alkyl lithium reagents such as n-butyl lithium or t-butyl Reacted with lithium, followed by a boronic acid ester, such as for example B (isopropoxy) ₃ , B (methoxy) ₃ or

It can be prepared by reacting with (see Synthesis (2000) 442-446).

와 반응시킴으로써 제조될 수 있다 (J. Org. Chem. 73 (2008) 2176-2181).Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups also react dibenzofuran, dibenzothiophene and carbazole with lithium amides such as lithium diisopropylamide (LDA) And then boronic acid esters such as B (isopropoxy) ₃ , B (methoxy) ₃ or

It can be prepared by reacting with (J. Org. Chem. 73 (2008) 2176-2181).

은 용매 중에서 촉매의 존재 하에 등몰량의 할로겐화 디벤조푸란, 디벤조티오펜, 카르바졸 및 4H-이미다조[1,2-a]이미다졸, 예컨대 예를 들어

와 반응시킬 수 있다. 촉매는 μ-할로(트리이소프로필포스핀)(η³-알릴)팔라듐(II) 유형 중 하나일 수 있다 (예를 들어, WO99/47474 참조).Dibenzofuran, dibenzothiophene and carbazole containing diboronic acid or diboronate groups, such as, for example

Equivalent amounts of halogenated dibenzofuran, dibenzothiophene, carbazole and 4H-imidazo[1,2-a]imidazole in the presence of a catalyst in a silver solvent such as, for example

Can react with. The catalyst may be of the μ-halo (triisopropylphosphine) (η ³ -allyl) palladium(II) type (see eg WO99/47474).

(여기서,

임)로 이루어진 군으로부터 선택된 리간드의 첨가가 바람직하다. 리간드는 Pd를 기준으로 하여 1:1 내지 1:10의 비로 첨가된다. 또한 바람직하게는, 촉매는 용액 또는 현탁액 중으로서 첨가된다. 바람직하게는, 적절한 유기 용매, 예컨대 상기 기재된 것, 바람직하게는 벤젠, 톨루엔, 크실렌, THF, 디옥산, 보다 바람직하게는 톨루엔 또는 이들의 혼합물이 사용된다. 용매의 양은 통상적으로 보론산 유도체의 몰당 1 내지 10 l 범위에서 선택된다. 유기 염기, 예컨대 예를 들어 테트라알킬암모늄 히드록시드, 및 상 이동 촉매, 예컨대 예를 들어 TBAB는 붕소의 활성을 촉진시킬 수 있다 (예를 들어, 문헌 [Leadbeater & Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407] 및 그에 인용된 참고문헌 참조). 반응 조건의 다른 변형은 문헌 [T. I. Wallow and B. M. Novak, J. Org. Chem. 59 (1994) 5034-5037; 및 M. Remmers, M. Schulze, G. Wegner, Macromol. Rapid Commun. 17 (1996) 239-252 및 G. A. Molander und B. Canturk, Angew. Chem. , 121 (2009) 9404 - 9425]에 주어져 있다.Preferably, the Suzuki reaction is in the presence of an organic solvent, such as an aromatic hydrocarbon or a conventional polar organic solvent, such as benzene, toluene, xylene, tetrahydrofuran or dioxane, or mixtures thereof, most preferably toluene. Is performed. Typically, the amount of solvent is selected from 1 to 10 l per mole of boronic acid derivative. Also preferably, the reaction is carried out under an inert atmosphere, such as nitrogen or argon. Additionally, it is preferred to carry out the reaction in the presence of an aqueous base, such as an alkali metal hydroxide or carbonate, such as NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ , Cs ₂ CO ₃ , and preferably The aqueous K ₂ CO ₃ solution is selected. Typically, the molar ratio of base to boronic acid or boronic acid ester derivative is selected in the range from 0.5:1 to 50:1, very particularly 1:1. Generally, the reaction temperature is selected in the range of 40 to 180°C, preferably under reflux conditions. Preferably, the reaction time is selected from 1 to 80 hours, more preferably from 20 to 72 hours. In a preferred embodiment, conventional catalysts for coupling reactions or polycondensation reactions are used, preferably Pd-based catalysts, which are described in WO2007/101820. The palladium compound is added in a ratio of 1:10000 to 1:50, preferably 1:5000 to 1:200, based on the number of bonds to be closed. For example, the use of palladium(II) salts such as PdAc ₂ or Pd ₂ dba ₃ and

(here,

Preferred is the addition of a ligand selected from the group consisting of Im). The ligand is added in a ratio of 1:1 to 1:10 based on Pd. Also preferably, the catalyst is added as a solution or suspension. Preferably, suitable organic solvents are used, such as those described above, preferably benzene, toluene, xylene, THF, dioxane, more preferably toluene or mixtures thereof. The amount of solvent is usually selected from 1 to 10 l per mole of boronic acid derivative. Organic bases such as tetraalkylammonium hydroxide, and phase transfer catalysts such as TBAB, for example, can promote the activity of boron (see, eg, Leadbeater &Marco; Angew. Chem. Int. Ed. Eng. 42 (2003) 1407 and references cited therein). Other variations of reaction conditions are described in TI Wallow and BM Novak, J. Org. Chem. 59 (1994) 5034-5037; And M. Remmers, M. Schulze, G. Wegner, Macromol. Rapid Commun. 17 (1996) 239-252 and GA Molander und B. Canturk, Angew. Chem. , 121 (2009) 9404-9425.

Synthesis of aza- and diaza-dibenzofuran starting materials is known in the literature or can be carried out analogously to known procedures.

JP2011084531 describes, for example, the synthesis of benzofuro[3,2-b]pyridine using base catalyzed cyclization in two steps starting from 2-bromopyridin-3-ol. The bromination compound is obtained by bromination with bromine in the presence of silver sulfate.

US2010/0187984 synthesizes 3,6-dichloro-benzofuro[2,3-b]pyridine using cyclization of a diazonium salt in three steps, for example starting from 2-amino-5-chloropyridine It describes.

[L. Kaczmarek, Polish Journal of Chemistry 59 (1985) 1141] uses furo[3,2- using acid catalyzed cyclization of diazonium salts starting from 2-(3-amino-2-pyridyl)pyridin-3-amine. It has been described to synthesize b:4,5-b]dipyridine.

JP2002284862 is a 2,7-dibro using acid catalyzed cyclization of diazonium salt starting from 2-(3-amino-5-bromo-2-pyridyl)-5-bromo-pyridin-3-amine It describes the synthesis of parent-furo[3,2-b:4,5-b]dipyridine. The synthesis of starting materials is described in [Y. Fort, Tetrahedron 50 (41), 11893 (1994).

[J. Liu, J. Org. Chem. 73, 2951 (2008) describe the synthesis of benzofuro[2,3-c]pyridine using, for example, a copper catalyzed cyclization step.

The possible synthetic routes for Compound E-57 are shown in the scheme below:

The possible synthetic routes for Compound A-11 are shown in the scheme below:

Halogen/metal exchange is carried out with nBuLi/THF at -78°C, or tBuLi/THF at -78°C. See WO2010/079051, where the synthesis of such compounds is described.

The compounds of formula (II) below are novel intermediates in the preparation of compounds of formula (I) and form a further subject of the invention.

(II)

(II)

B ¹ is N or CR ⁸¹ ,

B ² is N or CR ⁸² ,

B ³ is N or CR ⁸³ ,

B ⁴ is N or CR ⁸⁴ ,

B ⁵ is N or CR ⁸⁵ ,

B ⁶ is N or CR ⁸⁶ ,

B ⁷ is N or CR ⁸⁷ ,

B ⁸ is N or CR ⁸⁸ , wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ independently of each other can be substituted by H, optionally E and/or D C ₁ -C ₂₅ alkyl group which may be interposed; A C ₆ -C ₂₄ aryl group optionally substituted by G, a C ₂ -C ₃₀ heteroaryl group optionally substituted by G; Formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ or -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) a group of _r -X ¹ ,

o is 0 or 1, p is 0 or 1, q is 0 or 1, r is 0 or 1,

At least one of the substituents R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ is of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -( A ⁴ ) represents a group of _r -X ¹ ; here

, -BF₄Na 또는 -BF₄K (여기서 Y¹은 각 경우에 독립적으로 C₁-C₁₈알킬 기이고, Y²는 각 경우에 독립적으로 C₂-C₁₀알킬렌 기이고, Y¹³ 및 Y¹⁴는 서로 독립적으로 수소 또는 C₁-C₁₈알킬 기임)이고, o, p, q, r, G, A¹, A², A³, A⁴, R⁸¹, R⁸², R⁸³, R⁸⁴, R⁸⁵, R⁸⁶, R⁸⁷ 및 R⁸⁸은 상기 정의된 바와 같다. 하기 화합물은 선행 기술로부터 공지되어 있으며, 제외된다:X ¹ is Cl, Br or I, ZnX ¹² (X ¹² is a halogen atom); -SnR ²⁰⁷ R ²⁰⁸ R ²⁰⁹ (where R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ are the same or different, H or C ₁ -C ₈ alkyl, where the two radicals optionally form a common ring, and these radicals are Optionally branched or unbranched); -B(OH) ₂ , -B(OY ¹ ) ₂ ,

, -BF ₄ Na or -BF ₄ K (where Y ¹ is independently a C ₁ -C ₁₈ alkyl group in each case, Y ² is a C ₂ -C ₁₀ alkylene group independently in each case, Y ¹³ and Y ¹⁴ are independently of each other hydrogen or a C ₁ -C ₁₈ alkyl group), o, p, q, r, G, A ¹ , A ² , A ³ , A ⁴ , R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ are as defined above. The following compounds are known and excluded from the prior art:

.

.

R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ , A ¹ , For A ² , A ³ , A ⁴ and R ¹⁶ it is in principle preferred to be the same as in the case of the compounds of formula (I).

인 화학식 (II)의 화합물이 바람직하다.When X ¹ is Cl, Br or I, p is 0, q is 0 and r is 0; _{O in the} group of at least one formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -X ¹ is preferably 1. X ¹ is -B(OH) ₂ , -B(OY ¹ ) ₂ ,

Preference is given to compounds of formula (II).

Among the compounds of formula (II), the formula

Compounds of are preferred, wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁵ , R ⁸⁶ and R ⁸⁷ have the meanings given above.

In a preferred embodiment of the invention, the substituents R ⁸¹ , R ⁸² , R ⁸³ in the compounds of formula (II'), (II"), (II"'), (II"") and (II""') , R ⁸⁵ , one of R ⁸⁶ and R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -X ¹ .

In another preferred embodiment of the invention, the substituents R ⁸¹ , R ⁸² in the compounds of the formulas (II'), (II"), (II"'), (II"") and (II""'), Two of R ⁸³ , R ⁸⁵ , R ⁸⁶ and R ⁸⁷ are groups of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -X ¹ .

In a preferred embodiment, the invention relates to compounds of the formula

In the above formula, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁵ , R ⁸⁶ and R ⁸⁷ are as defined above.

In a preferred embodiment of the invention, formulas (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIg), (IIh), (IIi), (IIj), ( Substituents R ⁸¹ , R ⁸² , R ⁸³ in compounds of IIk), (IIl), (IIm), (IIn) and (IIo) One of R ⁸⁵ , R ⁸⁶ and R ⁸⁷ is a group of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -X ¹ .

In another preferred embodiment of the invention, the formulas (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIg), (IIh), (IIi), (IIj) , Substituents R ⁸¹ , R ⁸² , R ⁸³ in the compounds of (IIk), (IIl), (IIm), (IIn) and (IIo), Two of R ⁸⁵ , R ⁸⁶ and R ⁸⁷ are groups of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -X ¹ .

Compounds of formulas (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIi), (IIj), (IIl) and (IIn) are preferred. Particular preference is given to compounds of the formulas (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIj) and (IIn).

Examples of intermediates are shown below:

Bromidation of azadibenzofuran is described, for example, in J. Mater. Chem. 18 (2008) 1296-1301].

Other bromination methods are described, for example, in Helvetica Chimica Acta 89 (2006) 1123 and SYNLETT. 17 ( 2006) 2841-2845. 10.206.

Selective halogenation of (III) with halogenating agents results in compounds of formula (II). Halogenating agents include, for example, N-chlorosuccinimide (NCS), (Synlett 18 (2005) 2837-2842); Br ₂ (Synthesis 10 (2005) 1619-1624), N-bromosuccinimide (NBS) (Organic Letters 12 (2010) 2194-2197; Synlett (2006) 2841-2845), 1,3-dibromo -5,5-dimethylhydantoin (DBH) (Organic Process Research & Development 10 (2006) 822-828, US2002/0151456), CuBr ₂ (Synthetic Communications 37 (2007) 1381-1388); R ₄ NBr ₃ (Can. J. Chem. 67 (1989) 2062), N-iodosuccinimide (NIS) (Synthesis 12 (2001) 1794-1799, J. Heterocyclic Chem. 39 (2002) 933), KI/KIO ₃ (Org. Lett. 9 (2007) 797, Macromolecules 44 (2011) 1405-1413), NaIO ₄ /I ₂ /H ₂ SO ₄ or NaIO ₄ /KI/H ₂ SO ₄ (J. Heterocyclic Chem 38 (2001) 77; J. Org. Chem. 75 (2010) 2578-2588); Iodine monochloride (ICl; Synthesis (2008) 221-224). Additional methods are described in J. Org. Chem. 74 (2009) 3341-3349; J. Org. Chem. 71 (2006) 7422-7432, Eur. J. Org. Chem. (2008) 1065-1071, Chem. Asian J. 5 (2010) 2162-2167, Synthetic. Commun. 28 (1998) 3225.

Examples of solvents that can be used for halogenation are dimethylformamide (DMF), CH ₂ Cl ₂ , CHCl ₃ , CCl ₄ , ethanol (EtOH), acetic acid (AcOH), H ₂ SO ₄ , C ₆ H ₅ Cl and their It is a mixture. Halogenation can be carried out in the presence of an acid and a Lewis acid, such as for example H ₂ SO ₄ , ZrCl ₄ , TiCl ₄ , AlCl ₃ , HfCl ₄ and AlCl ₃ (Synlett 18 (2005) 2837-2842).

와 반응시킴으로써 보론산에스테르 중간체 (II)로 전환될 수 있다 (문헌 [Prasad Appukkuttan et al., Synlett 8 (2003) 1204] 참조).Halogenated intermediate (II) wherein X ³ is Cl, Br or I is a catalyst such as [1,1′-bis] in a solvent such as dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene. (Diphenylphosphino)ferrocene]dichloropalladium(II), complex (Pd(Cl) ₂ (dppf)), and halogenated intermediate (II) in the presence of a base such as potassium acetate (Y ¹ O) ₂ BB(OY ¹ ) ₂ ,

Can be converted to boronic acid ester intermediate (II) (see Prasad Appukkuttan et al., Synlett 8 (2003) 1204).

An overview of the preparation of boronic acid reagents is described in Angew. Chem. 121 (2009) 9404-9425, Chem. Rev. 95 (1995) 2457-2483, Angew. Chem. Int. Ed. 41 (2002) 4176-4211, Tetrahedron 66 (2010) 8121-8136.

와 반응시킴으로써 제조될 수 있다 (문헌 [Synthesis (2000) 442-446] 참조).The diboronic acid or diboronate intermediate (II) also reacts the halogenated intermediate (II) with an alkyl lithium reagent such as n-butyl lithium or t-butyl lithium, followed by a boronic acid ester such as B( Isopropoxy) ₃ , B (methoxy) ₃ or

It can be prepared by reacting with (see Synthesis (2000) 442-446).

The compounds of formula (I) can be obtained from intermediates and suitable co-reactants, for example by Suzuki-, Still- or Negishi-coupling reactions.

는 용매, 예컨대 예를 들어 디메틸 포름아미드, 디메틸 술폭시드, 디옥산 및/또는 톨루엔 중에서 촉매, 예컨대 예를 들어 [1,1'-비스(디페닐포스피노)페로센]디클로로팔라듐(II), 착물 (Pd(Cl)₂(dppf)), 및 염기, 예컨대 예를 들어 아세트산칼륨의 존재 하에 중간체 (N-2)를 X²-(A¹)_o-(A²)_p-(A³)_q-(A⁴)_r-R¹⁶ (여기서, X²는 (Y¹O)₂B-,

임)과 반응시킴으로써 화학식 (I)의 화합물로 전환될 수 있다 (문헌 [Prasad Appukkuttan et al., Synlett 8 (2003) 1204] 참조).Halogenated intermediates wherein X ¹ is Cl, Br or I, for example

Is a catalyst such as [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), complex, for example in a solvent such as dimethyl formamide, dimethyl sulfoxide, dioxane and/or toluene (Pd(Cl) ₂ (dppf)), and intermediate (N-2) in the presence of a base such as, for example, potassium acetate, X ² -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ (where X ² is (Y ¹ O) ₂ B-,

It can be converted to a compound of formula (I) by reacting with Im) (see Prasad Appukkuttan et al., Synlett 8 (2003) 1204).

The compounds of formula (I) are particularly suitable for use in applications where charge carrier conductivity is required, in particular for example switching elements such as organic transistors such as organic FETs and organic TFTs, organic solar cells and organic light emitting diodes (OLEDs). Suitable for use in organic electronics applications selected from ), the compound of formula (I) as a matrix material in the light emitting layer and/or as a hole and/or exciton blocker material and/or as an electron and/or exciton blocker material , Especially in OLEDs for use in combination with phosphorescent emitters. When the compounds of the formula (I) of the present invention are used in OLEDs, OLEDs are obtained which have good efficiency and long life and can be operated especially at low use and operating voltage. The compounds of formula (I) of the present invention are particularly suitable for use as matrix and/or hole/exciter blocker materials for blue and green emitters, for example blue or dark blue emitters (these are particularly phosphor emitters). Do. In addition, the compounds of formula (I) can be used as conductors/supplementary materials in organic electronics applications selected from switching elements and organic solar cells.

Compounds of formula (I), especially formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ii), (Ij), (Il) and (In) are organic Matrix materials and/or hole/exciter blocker materials and/or electron/exciter blocker materials and/or hole inject materials and/or electron inject materials and/or hole conductor materials (hole transport materials) and/or in electronics applications, especially in OLEDs, and/or Or as an electron conductor material (electron transport material), preferably as a matrix material and/or electron/exciton blocker and/or hole transport material. The compounds of formula (I) of the present invention are more preferably used as matrix materials in organic electronics applications, especially OLEDs.

In either the emissive layer or the emissive layers of the OLED, it is also possible to combine the emitter material with the matrix material of the compound of formula (I), and further matrix material with good hole conductor (hole transport) properties, for example. . High quantum efficiency of this emitting layer is thereby achieved.

Certain compounds of formula (I), for example G-1, have an ionization potential of greater than 6 eV and are therefore suitable as electron transport materials.

When the compound of formula (I) is used as a matrix material in the emitting layer and additionally as a hole/exciter blocker material and/or an electron/exciter blocker material, due to the chemical identity or similarity of the material, adjacent holes/ An improved interface between the exciton blocker material and/or the electron/exciter blocker material is obtained, which can lead to a reduction in voltage with equivalent brightness and an extension of the lifetime of the OLED. Moreover, the use of the same material for the hole/exciter blocker material and/or for the electron/exciter blocker material, and for the matrix of the emission layer allows simplification of the manufacturing process of the OLED, which has the same source of compound of formula (I) This is because one of the materials can be used in the deposition process.

Suitable structures for organic electronic devices are known to the skilled person and are specified below.

The organic transistor generally includes a semiconductor layer formed from an organic layer having hole transport capability and/or electron transport capability; A gate electrode formed from a conductive layer; And an insulating layer introduced between the semiconductor layer and the conductive layer. A transistor element is manufactured by mounting the source electrode and the drain electrode in this arrangement. In addition, additional layers known to those skilled in the art may be present in the organic transistor.

An organic solar cell (photoelectric conversion element) generally includes an organic layer present between two plate-shaped electrodes arranged in parallel. The organic layer can be constructed on a comb-shaped electrode. There are no specific restrictions with respect to the area of the organic layer, and there are no specific restrictions with respect to the material of the electrode. However, when plate-shaped electrodes arranged in parallel are used, at least one electrode is preferably formed from a transparent electrode, for example, an ITO electrode or a fluorine-doped tin oxide electrode. The organic layer is formed from two sub-layers, a layer with p-type semiconductor properties or hole transport capability, and a layer formed with n-type semiconductor properties or electron transport capability. It is also possible that additional layers known to those skilled in the art are present in the organic solar cell. The layer having hole transport ability may include a compound of formula (I).

It is likewise possible for the compound of formula (I) to be present in the light-emitting layer (preferably as a matrix material) as well as in the electron blocking layer (as an electron/exciton blocker).

The invention furthermore comprises anode An and cathode Ka, and a light emitting layer E arranged between anode An and cathode Ka, and where appropriate at least one blocking layer for holes/excitation, at least one blocking layer for electrons/excitation , Providing an organic light emitting diode comprising at least one additional layer selected from the group consisting of at least one hole injection layer, at least one hole conductor layer, at least one electron injection layer and at least one electron conductor layer, wherein At least one compound of formula (I) is present in the light emitting layer E and/or at least one further layer. The at least one compound of formula (I) is preferably present in the light emitting layer and/or hole blocking layer.

Additionally, the present application provides at least one compound of formula (I), in particular formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ii), (Ij), ( Il) or a compound of (In), very particularly compounds A-1 to A-65, B-1 to B-8, C-1 to C-65, D-1 to D-8, E-1 to E- 65, or F-1 to F-65.

Structure of OLED of the present invention

Therefore, the organic light emitting diode (OLED) of the present invention generally has the following structure:

Anode (An) and cathode (Ka), and a light emitting layer E arranged between anode (An) and cathode (Ka).

The OLED of the present invention can be formed from the following layers, for example-in a preferred embodiment:

1.Anode

2. Hole conductor layer

3. emitting layer

4. Hole/exciter blocking layer

5. Electronic conductor layer

6. Cathode

Layer sequences different from the above-mentioned structures are also possible, which are known to the skilled person. For example, OLEDs may not have all of the layers mentioned; OLEDs with for example layers (1) (anode), (3) (light emitting layer) and (6) (cathode) are likewise suitable, in which case layers 2 (hole conductor layer) and (4) ( It is possible that the functions of the hole/excitation blocking layer) and (5) (electronic conductor layer) are performed by adjacent layers. OLEDs having layers (1), (2), (3) and (6), or layers (1), (3), (4), (5) and (6) are likewise suitable. Further, the OLED may have an electron/excitation blocking layer between the hole conductor layer 2 and the light emitting layer 3.

Additionally, a plurality of the above-mentioned functions (electron/exciter blocker, hole/exciter blocker, hole injection, hole conduction, electron injection, electron conduction) are combined in one layer, which is for example a single substance present in this layer It is possible to be done by. For example, the material used in the hole conductor layer can, in one embodiment, block excitons and/or electrons simultaneously.

Also, individual layers of OLEDs among those specified above may be formed again from two or more layers. For example, the hole conductor layer can be formed from a layer from which holes are injected from the electrode, and a layer that transports holes from the hole-injection layer into the light emitting layer. The electron conducting layer can likewise consist of a plurality of layers, for example a layer in which electrons are injected by an electrode, and a layer that receives electrons from the electron injection layer and transports them into the light emitting layer. These layers mentioned are selected according to factors such as energy level, thermal resistance and charge carrier mobility, and also the energy difference of the layer specified by the organic layer or metal electrode. The person skilled in the art can select the structure of the OLED in order to optimally conform to the organic compounds used as emitter materials according to the invention.

In order to obtain a particularly efficient OLED, for example, the HOMO (highest occupied molecular orbital) of the hole conductor layer must conform to the working function of the anode, and the LUMO (lowest non-occupied molecular orbital) of the electron conductor layer is the working function of the cathode. The layer mentioned above is present in the OLED of the present invention.

The anode 1 is an electrode that provides a positive charge carrier. It can be formed from materials comprising, for example, metals, mixtures of various metals, metal alloys, metal oxides or mixtures of various metal oxides. Alternatively, the anode can be a conductive polymer. Suitable metals include main group metals, transition metals and lanthanoids, especially metals of groups Ib, IVa, Va and VIa of the periodic table of elements, and metals and alloys of transition metals of group VIIIa. In cases where the anode should be transparent, mixed metal oxides of groups IIb, IIIb and IVb of the Periodic Table of the Elements (IUPAC version) are generally used, such as indium tin oxide (ITO). Similarly, the anode (1) is described, for example, in Nature, Vol. 357, pages 477 to 479 (June 11, 1992). It is possible to include organic materials, such as polyaniline. At least one of the anode or cathode must be at least partially transparent so that it is possible to emit the formed light. The material used for the anode 1 is preferably ITO.

Hole conductor materials suitable for the layer (2) of the OLED of the present invention are described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 4th edition, Vol. 18, pages 837 to 860, 1996. Both hole-transporting molecules and polymers can be used as the hole-transporting material. The hole transport molecule typically used is tris[N-(1-naphthyl)-N-(phenylamino)]triphenylamine (1-NaphDATA), 4,4'-bis[N-(1-naphthyl) -N-phenylamino]biphenyl (α-NPD), N,N'-diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (TPD), 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (TAPC), N,N'-bis(4-methylphenyl)-N,N'-bis(4-ethylphenyl) -[1,1'-(3,3'-dimethyl)biphenyl]-4,4'-diamine (ETPD), tetrakis(3-methylphenyl)-N,N,N',N'-2,5 -Phenylenediamine (PDA), α-phenyl-4-N,N-diphenylaminostyrene (TPS), p-(diethylamino)benzaldehyde diphenylhydrazone (DEH), triphenylamine (TPA), bis [4-(N,N-diethylamino)-2-methylphenyl)(4-methylphenyl)methane (MPMP), 1-phenyl-3-[p-(diethylamino)styryl]-5-[p- (Diethylamino)phenyl]pyrazoline (PPR or DEASP), 1,2-trans-bis(9H-carbazole-9-yl)cyclobutane (DCZB), N,N,N',N'-tetrakis (4-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TTB), 4,4',4"-tris(N,N-diphenylamino)triphenylamine (TDTA) , 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA), N,N'-bis(naphthalen-2-yl)-N,N'-bis(phenyl)benzidine (β -NPB), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)-9,9-spirobifluorene (spiro-TPD), N,N'-bis(naphthalene-1 -Yl)-N,N'-bis(phenyl)-9,9-spirobifluorene (spiro-NPB), N,N'-bis(3-methylphenyl)-N,N'-bis(phenyl)- 9,9-dimethylfluorene (DMFL-TPD), di[4-(N,N-ditolylamino)phenyl]cyclohexane, N,N'-bis(naphthalen-1-yl)-N,N'- Bis(phenyl)-9,9-dimethylfluorene, N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-2,2-dimethylbenzidine, N,N'-bis (Naphthalen-1-yl)-N,N'-bis(phenyl)benzidine, N,N'-bis(3-methyl Phenyl)-N,N'-bis(phenyl)benzidine, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ), 4,4' ,4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine, 4,4',4"-tris(N-(2-naphthyl)-N-phenyl-amino)triphenylamine, Pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile (PPDN), N,N,N',N'-tetrakis(4-methoxyphenyl)benzidine ( MeO-TPD), 2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobifluorene (MeO-spiro-TPD), 2,2'-bis[N ,N-bis(4-methoxyphenyl)amino]-9,9-spirobifluorene (2,2'-MeO-spiro-TPD), N,N'-diphenyl-N,N'-di[ 4-(N,N-ditolylamino)phenyl]benzidine (NTNPB), N,N'-diphenyl-N,N'-di[4-(N,N-diphenylamino)phenyl]benzidine (NPNPB) , N,N'-di(naphthalen-2-yl)-N,N'-diphenylbenzene-1,4-diamine (β-NPP), N,N'-bis(3-methylphenyl)-N,N '-Bis(phenyl)-9,9-diphenylfluorene (DPFL-TPD), N,N'-bis(naphthalen-1-yl)-N,N'-bis(phenyl)-9,9-di Phenylfluorene (DPFL-NPB), 2,2',7,7'-tetrakis(N,N-diphenylamino)-9,9'-spirobifluorene (spiro-TAD), 9,9- Bis[4-(N,N-bis(biphenyl-4-yl)amino)phenyl]-9H-fluorene (BPAPF), 9,9-bis[4-(N,N-bis(naphthalene-2- 1)amino)phenyl]-9H-fluorene (NPAPF), 9,9-bis[4-(N,N-bis(naphthalen-2-yl)-N,N'-bisphenylamino)phenyl]-9H -Fluorene (NPBAPF), 2,2',7,7'-tetrakis[N-naphthalenyl(phenyl)amino]-9,9'-spirobifluorene (spiro-2NPB), N,N' -Bis(phenanthrene-9-yl)-N,N'-bis(phenyl)benzidine (PAPB), 2,7-bis[N,N-bis(9,9-spirobifluoren-2-yl) Amino]-9,9-spirobifluorene (spiro-5), 2,2'-bis[N,N-bis(biphenyl-4-yl)amino]-9,9-spirobifluorene (2 ,2'-spiro-DBP), 2,2'-bis(N,N-diphenylamino)-9,9-spirobifluorene (spiro-BPA), 2,2',7,7'-tetra (N,N-Ditolyl)aminospirobifluorene (spiro-TTB), N,N,N',N'-tetranaphthalene-2-ylbenzidine (TNB), porphyrin compounds and phthalocyanines, such as copper phthalocyanine and oxidation Titanium phthalocyanine. The hole-transport material typically used is selected from the group consisting of polyvinylcarbazole, (phenylmethyl)polysilane and polyaniline. It is likewise possible to obtain hole-transporting polymers by doping hole-transporting molecules into polymers such as polystyrene and polycarbonate. Suitable hole-transporting molecules are those already mentioned above.

을 갖는 Ir(dpbic)₃이고, 이는 예를 들어 WO2005/019373에 개시되어 있다. 원칙적으로, 정공 전도체 층이 정공 전도체 물질로서 적어도 하나의 화학식 (I)의 화합물, 특히 화학식 (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ii), (Ij), (Il) 또는 (In)의 화합물, 매우 특히 화합물 A-1 내지 A-65, B-1 내지 B-8, C-1 내지 C-65, D-1 내지 D-8, E-1 내지 E-65, 또는 F-1 내지 F-65를 포함하는 것이 가능하다.It is also possible-in one embodiment-to use the carbene complex as a hole conductor material, and the band gap of the at least one hole conductor material is generally larger than the band gap of the emitter material used. In the context of the present application, “band gap” is understood to mean triplet energy. Suitable carbene complexes are, for example, carbene complexes as described in WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727. One example of a suitable carbene complex is the formula

Ir(dpbic) ₃ , which is disclosed, for example, in WO2005/019373. In principle, the hole conductor layer is a hole conductor material, at least one compound of formula (I), in particular formulas (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ii) , Compounds of (Ij), (Il) or (In), very particularly compounds A-1 to A-65, B-1 to B-8, C-1 to C-65, D-1 to D-8, It is possible to include E-1 to E-65, or F-1 to F-65.

The hole-transport layer can also be electronically doped primarily to make the layer thickness more generous (pinhole/short circuit protection), and to minimize the operating voltage of the device, thereby improving the transport properties of the materials used. Electronic doping is known to those skilled in the art, see, eg, W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, 2003, 359 (p-doped organic layer); AG Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, number 25, 2003, 4495 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103, and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example, it is possible to use mixtures in the hole-transport layer, in particular mixtures that cause electrical p-doping of the hole-transport layer. P-doping is achieved by the addition of oxidizing materials. These mixtures are, for example, the following mixtures: the above-mentioned hole transport material and at least one metal oxide, for example MoO ₂ , MoO ₃ , WO _x , ReO ₃ and/or V ₂ O ₅ , preferably MoO ₃ And/or a mixture of ReO ₃ , more preferably MoO ₃ , or the hole transport material mentioned above, 7,7,8,8-tetracyanoquinodimethane (TCNQ), 2,3,5,6- Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F ₄ -TCNQ), 2,5-bis(2-hydroxyethoxy)-7,7,8,8-tetracyano Quinodimethane, bis(tetra-n-butylammonium)tetracyanodiphenoquinodimethane, 2,5-dimethyl-7,7,8,8-tetracyanoquinodimethane, tetracyanoethylene, 11,11 ,12,12-tetracyanonaphtho2,6-quinodimethane, 2-fluoro-7,7,8,8-tetracyanoquino-dimethane, 2,5-difluoro-7,7, 8,8 Etracyanoquinodimethane, dicyanomethylene-1,3,4,5,7,8-hexafluoro-6Hnaphthalene- _2- ylide)malononitrile (F ₆ -TNAP), Mo( tfd) ₃ (from Kahn et al., J. Am. Chem. Soc. 2009, 131 (35), 12530-12531), EP1988587, US2008265216, EP2180029, US20100102709, WO2010132236, EP2180029 It may be a mixture comprising a compound and one or more compounds selected from quinone compounds as mentioned in EP2401254. Preferred mixtures include the above-mentioned carbene complexes, for example the carbene complex HTM-1, and MoO ₃ and/or ReO ₃ , in particular MoO ₃ . In a particularly preferred embodiment, the hole transport layer comprises 0.1 to 10% by weight of MoO ₃ and 90 to 99.9% by weight of the carbene complex, in particular the carbene complex HTM-1, wherein the total amount of MoO ₃ and carbene complex is 100% by weight.

The luminescent layer 3 comprises at least one emitter material. In principle, it can be a fluorescent or phosphorescent emitter, and suitable emitter materials are known to the skilled person. The at least one emitter material is preferably a phosphorescent emitter. The phosphorescent emitter compounds preferably used are based on metal complexes, in particular complexes of metals Ru, Rh, Ir, Pd and Pt, especially complexes of Ir, which have increased in importance. The compound of formula (I) can be used as a matrix in the light emitting layer.

Metal complexes suitable for use in the OLED of the present invention include, for example, documents WO02/60910A1, US2001/0015432A1, US2001/0019782A1, US2002/0055014A1, US2002/0024293A1, US2002/0048689A1, EP1191612A2, EP1191613A2, EP1211257A2, US2002/00944531 , WO02/02714A2, WO00/70655A2, WO01/41512A1, WO02/15645A1, WO2005/019373A2, WO2005/113704A2, WO2006/115301A1, WO2006/067074A1, WO2006/056418, WO2006121811A1, WO2007095118A2, WO2007/115970, WO2008/115981 /000727, WO2010129323, WO2010056669, WO10086089, US2011/0057559, WO2011/106344, US2011/0233528, WO2012/048266 and WO2012/172482.

Additional suitable metal complexes are commercially available metal complex tris(2-phenylpyridine)iridium(III), iridium(III) tris(2-(4-tolyl)pyridine-N,C ^2' ), bis (2-phenylpyridine)(acetylacetonato) iridium(III), iridium(III) tris(1-phenylisoquinoline), iridium(III) bis(2,2'-benzothienyl)pyridine- N,C ^3' )(acetylacetonate), tris(2-phenylquinoline) iridium(III), iridium(III) bis(2-(4,6-difluorophenyl)pyridine-N,C ² ) Picolinate, iridium(III) bis(1-phenylisoquinoline)(acetylacetonate), bis(2-phenylquinoline)(acetylacetonato)iridium(III), iridium(III) bis(di- Benzo[f,h]quinoxaline) (acetylacetonate), iridium(III) bis(2-methyldi-benzo[f,h]quinoxaline) (acetylacetonate) and tris(3-methyl-1-phenyl) -4-trimethylacetyl-5-pyrazolino)terbium(III), bis[1-(9,9-dimethyl-9H-fluoren-2-yl)isoquinoline](acetylacetonato)iridium(III) , Bis(2-phenylbenzothiazolate)(acetylacetonato)iridium(III), bis(2-(9,9-dihexylfluorenyl)-1-pyridine)(acetylacetonato)iridium( III), bis(2-benzo[b]thiophen-2-yl-pyridine)(acetylacetonato)iridium(III).

In addition, the following commercially available materials are suitable: tris(dibenzoylacetonato)mono(phenanthroline)uropium(III), tris(dibenzoylmethane)-mono(phenanthroline)uropium(III), Tris (dibenzoylmethane) mono (5-aminophenanthroline) europium (III), tris (di-2-naphthoylmethane) mono (phenanthroline) europium (III), tris (4-bromobenzoylmethane) Mono (phenanthroline) europium (III), tris (di (biphenyl) methane) mono (phenanthroline) europium (III), tris (dibenzoylmethane) mono (4,7-diphenylphenanthroline) europium (III), tris (dibenzoylmethane) mono (4,7-di-methylphenanthroline) europium (III), tris (dibenzoylmethane) mono (4,7-dimethylphenanthroline disulfonic acid) europium (III) Disodium salt, tris[di(4-(2-(2-ethoxyethoxy)ethoxy)benzoylmethane)]mono(phenanthroline)uropium(III) and tris[di[4-(2-(2 -Ethoxyethoxy)ethoxy)benzoylmethane)]mono(5-aminophenanthroline)uropium(III), osmium(II) bis(3-(trifluoromethyl)-5-(4-tert-butyl) Pyridyl)-1,2,4-triazolito)diphenylmethylphosphine, osmium(II) bis(3-(trifluoromethyl)-5-(2-pyridyl)-1,2,4- Triazole)dimethylphenylphosphine, osmium(II) bis(3-(trifluoromethyl)-5-(4-tert-butylpyridyl)-1,2,4-triazoleito)dimethylphenylphosphine, Osmium(II) bis(3-(trifluoromethyl)-5-(2-pyridyl)pyrazolato)dimethylphenylphosphine, tris[4,4'-di-tert-butyl(2,2') -Bipyridine]ruthenium(III), osmium(II) bis(2-(9,9-dibutylfluorenyl)-1-isoquinoline (acetylacetonate).

The preferred phosphorescent emitter is a carbene complex. Suitable phosphorescent blue emitters are specified in the following publications: WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981, WO2008/000727, WO2009050281, WO2009050290, WO2011051404, US2011/057559, WO2011/073149, WO2012/ 121936A2, US2012/0305894A1, WO2012/170571, WO2012/170461, WO2012/170463, WO2006/121811, WO2007/095118, WO2008/156879, WO2008/156879, WO2010/068876, US2011/0057559, WO2011/106344, US2011/0233528, WO2012/048266 and WO2012/172482.

The light emitting layer preferably comprises a compound of the formula [L] _m1 [K] _o1 M[carben] _n1 (IX) described in WO 2005/019373A2, wherein the symbol has the following meaning:

M is Co, Rh, Ir, Nb, Pd, Pt, Fe, Ru, Os, Cr, Mo, W, M _n , Tc, Re, Cu, Ag and Au in any oxidation state possible for each metal atom A metal atom selected from the group consisting of;

Carbenes are uncharged or monoanionic, and carbene ligands that can be monodentate, bidentate or tridentate, and carbene ligands can also be biscarbene or triscarbene ligands;

L is a monoanionic or anionic ligand, which may be monodentate or bidentate;

K is phosphine; Phosphonates and derivatives thereof, arsenate and derivatives thereof; Phosphite; CO; Pyridine; An uncharged monodentate or bidentate ligand selected from the group consisting of nitriles and conjugated dienes forming π complexes with M ¹ ;

n1 is the number of carbene ligands, where n1 is at least 1, and when n1> 1, the carbene ligands in the complex of formula (IX) may be the same or different;

m1 is the number of ligands L, where m1 can be 0 or ≥ 1, and when m1> 1 the ligands L can be the same or different;

o1 is the number of ligands K, where o1 can be 0 or ≥ 1, and when o> 1, ligand K can be the same or different;

Here, the sum of n1 + m1 + o1 depends on the oxidation state and coordination number of the metal atom, and on the number of digits of the ligands carbene, L and K, and also on the charge of the ligands, carbene and L n1 is at least 1.

Suitable triple emitter carbene complexes are described, for example, in WO 2006/056418 A2, WO 2005/113704, WO 2007/115970, WO 2007/115981 and WO 2008/000727, WO2009050281, WO2009050290, WO2011051404 and WO2011073149.

Metal-carbene complexes of the formula (IXa) described below in U.S. Patent Application Nos. 61/286046, 61/323885 and European Patent Application 10187176.2 (PCT/EP2010/069541) are more preferred.

(IXa)

(IXa)

In the above formula, M, n1, Y, A ^2' , A ^3' , A ^4' , A ^5' , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ , R ⁵⁸ , R ⁵⁹ , K, L, m1 and o1 are each defined as follows:

M is Ir or Pt,

n1 is an integer selected from 1, 2 and 3,

Y is NR ⁵¹ , O, S or C(R ²⁵ ) ₂ ,

A ^2' , A ^3' , A ^4'and A ^5'are each independently N or C, where 2 A = nitrogen atoms, and at least one carbon atom is between two nitrogen atoms in the ring,

R ⁵¹ is optionally a linear or branched alkyl radical having 1 to 20 carbon atoms, optionally having at least one heteroatom interposed and optionally having at least one functional group, at least one heteroatom optionally interposing and optionally having at least one functional group And a cycloalkyl radical having 3 to 20 carbon atoms, at least one heteroatom optionally interposed, optionally having at least one functional group, and a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, at least one heteroatom Is a substituted or unsubstituted heteroaryl radical optionally interrupted and optionally having at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,

R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ are each a free electron pair when A ^2' , A ^3' , A ^4'and /or A ^5'is N, or A ^2' , A ^3' , When A ^4'and /or A ^5'is C, each independently hydrogen, a linear or branched alkyl radical having at least one heteroatom, optionally having at least one functional group and having 1 to 20 carbon atoms, A cycloalkyl radical having 3 to 20 carbon atoms, optionally having at least one heteroatom, optionally having at least one functional group, at least one heteroatom, optionally having at least one functional group, and 6 to 30 carbon atoms A substituted or unsubstituted aryl radical having at least one heteroatom optionally substituted and optionally having at least one functional group and having 5 to 18 carbon atoms and/or heteroatoms in total, a substituted or unsubstituted heteroaryl radical, a donor Or a group with acceptor action, or

R ⁵³ and R ⁵⁴ forms a A ^{3 'and} A ^4' and with at least one additional hetero atom is optionally interposed optionally substituted with 5 to 18 carbon atoms and / or heteroatoms, the total unsaturated ring,

R ⁵⁶ , R ⁵⁷ , R ⁵⁸ and R ⁵⁹ are each independently hydrogen, a linear or branched alkyl radical having at least one functional group, optionally having at least one functional group and having 1 to 20 carbon atoms, at least A cycloalkyl radical having 3 to 20 carbon atoms optionally having one heteroatom interposed and optionally having at least one functional group, at least one heteroatom optionally having at least one functional group optionally having 3 to 20 carbon atoms, Having a cycloheteroalkyl radical, optionally substituted with at least one heteroatom, optionally having at least one functional group, and a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, at least one heteroatom optionally interposed and at least one functional group Or a substituted or unsubstituted heteroaryl radical having a total of 5 to 18 carbon atoms and/or heteroatoms, a group having donor or acceptor action, or

R ⁵⁶ and R ⁵⁷ , R ⁵⁷ and R ⁵⁸ , or R ⁵⁸ and R ⁵⁹ together with the carbon atom to which they are attached, have at least one heteroatom optionally interrupted and have a total of 5 to 18 carbon atoms and/or heteroatoms Form an optionally substituted saturated, unsaturated or aromatic ring, and/or

When A ^5′ is C, R ⁵⁵ and R ⁵⁶ together are saturated, optionally containing heteroatoms, aromatic units, heteroaromatic units and/or functional groups and having 1 to 30 carbon atoms and/or heteroatoms in total, or Forming an unsaturated, linear or branched bridge, wherein a substituted or unsubstituted 5- to 8-membered ring containing carbon atoms and/or heteroatoms is optionally fused,

R ²⁵ is independently a linear or branched alkyl radical having at least one heteroatom optionally interposed and optionally having at least one functional group and having 1 to 20 carbon atoms, at least one heteroatom arbitrarily interposed and at least one functional group A cycloalkyl radical optionally having 3 to 20 carbon atoms, a substituted or unsubstituted aryl radical having 6 to 30 carbon atoms, optionally having at least one heteroatom, optionally having at least one functional group, at least one A heteroaryl radical optionally substituted with heteroatoms and optionally having at least one functional group and having a total of 5 to 18 carbon atoms and/or heteroatoms,

K is an uncharged monodentate or bidentate ligand,

L is a monoanionic or anionic ligand, preferably a monoanionic ligand, which may be monodentate or bidentate,

m1 is 0, 1 or 2, wherein when m1 is 2, the K ligand may be the same or different,

o1 is 0, 1 or 2, where L ligand can be the same or different when o1 is 2.

The compound of formula (IX) is preferably a compound of the formula:

.

.

Additional suitable non-carbene emitter materials are mentioned below:

의 화합물이다.The most preferred phosphorescent blue emitter is the chemical formula

It is a compound.

Alloligand metal-carbene complexes may exist in the form of a plane or meridional isomer, with a plane isomer being preferred.

In the case of a heteroligand metal-carbene complex, four different isomers may be present, with pseudo-surface isomers being preferred.

The light-emitting layer can include additional components in addition to the emitter material. For example, a fluorescent dye may be present in the light-emitting layer to change the emission color of the emitter material. Also-in preferred embodiments-matrix materials can be used. This matrix material can be a polymer, for example poly(N-vinylcarbazole) or polysilane. However, the matrix material can be a small molecule, for example 4,4'-N,N'-dicarbazolebiphenyl (CDP=CBP) or a tertiary aromatic amine, for example TCTA. In a preferred embodiment of the invention, at least one compound of formula (I) is used as matrix material.

In a preferred embodiment, the light emitting layer is 2 to 40% by weight, preferably 5 to 35% by weight, at least one of the above-mentioned emitter materials, and 60 to 98% by weight, preferably 75 to 95% by weight , Formed from at least one of the aforementioned matrix materials-in one embodiment at least one compound of formula (I)-wherein the sum of the emitter material and the matrix material is 100% by weight.

Compounds of formula (I) are especially those of formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ii), (Ij), (Il) or (In) , Very particularly A-1 to A-65, B-1 to B-8, C-1 to C-65, D-1 to D-8, E-1 to E-65, or F-1 to F- 65.

및 바람직하게는 화학식

의 2종의 카르벤 착물을 포함한다. 상기 실시양태에서, 발광 층은 2 내지 40 중량%, 바람직하게는 5 내지 35 중량%의

, 및 60 내지 98 중량%, 바람직하게는 65 내지 95 중량%의 화학식 (I) 및

의 화합물로부터 형성되고, 여기서 카르벤 착물 및 화학식 (I)의 화합물의 총합은 100 중량%이다.In a particularly preferred embodiment, the light emitting layer is a compound of formula (I), for example

And preferably a chemical formula

It contains two kinds of carbene complexes. In the above embodiment, the light emitting layer is 2 to 40% by weight, preferably 5 to 35% by weight

, And 60 to 98% by weight, preferably 65 to 95% by weight of formula (I) and

It is formed from a compound, wherein the total of the carbene complex and the compound of formula (I) is 100% by weight.

Accordingly, the matrix material and/or hole/exciter blocker material and/or electron/exciter blocker material and/or hole injection material and/or electron injection material and/or hole conductor material and/or in the OLED together with the compound of formula (I) and/or Or a metal complex suitable for use as an electron conductor material, preferably as a matrix material and/or hole/exciter blocker material, for example also WO 2005/019373 A2, WO 2006/056418 A2, WO 2005/113704, WO Carbene complexes as described in 2007/115970, WO 2007/115981 and WO 2008/000727. Here, the disclosures of the cited WO applications are explicitly referenced, and these disclosures should be considered to be included in the content of the present application.

The compounds of the invention can also be used as hosts for phosphorescent green emitters. Suitable phosphorescent green emitters are specified, for example, in the following publications: WO2006014599, WO20080220265, WO2009073245, WO2010027583, WO2010028151, US20110227049, WO2011090535, WO2012/08881, WO20100056669, WO20100118029, WO20100244004, WO2011109042, WO2012166608; US6687266, US20070190359, US20070190359, US20060008670; WO2006098460, US20110210316, WO 2012053627; US6921915, US20090039776; And JP2007123392.

Examples of suitable phosphorescent green emitters are shown below:

When a hole blocking layer is present-hole blocking materials typically used in OLEDs are, for example, 2,6-bis(N-carbazolyl)pyridine (mCPy), 2,9-dimethyl-4,7- Diphenyl-1,10-phenanthroline (Batocuproin, (BCP)), bis(2-methyl-8-quinolinate)-4-phenylphenylleato)aluminum(III) (BAlq), phe Nothiazine S,S-dioxide derivative and 1,3,5-tris(N-phenyl-2-benzylimidazolyl)benzene) (TPBI), TPBI is also suitable as an electron-conducting material. Further suitable hole blockers and/or electron conductor materials are 2,2',2"-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole), 2-(4-ratio Phenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, 8-hydroxyquinolinoleitolithium, 4-(naphthalen-1-yl)-3,5-diphenyl -4H-1,2,4-triazole, 1,3-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]benzene, 4,7-diphenyl-1,10-phenanthroline, 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole, 6,6'- Bis[5-(biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2'-bipyridyl, 2-phenyl-9,10-di(naphthalene-2 -Yl)anthracene, 2,7-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]-9,9-dimethylfluorene, 1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene, 2-(naphthalen-2-yl)-4,7-diphenyl- 1,10-phenanthroline, tris-(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane, 2,9-bis(naphthalen-2-yl)-4,7-di Phenyl-1,10-phenanthroline, 1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazo[4,5-f][1,10]-phenanthroline In a further embodiment, comprising an aromatic or heteroaromatic ring bonded via a group comprising a carbonyl group as disclosed in WO2006/100298, as a hole/exciter blocking layer 4 or as a matrix material in the light emitting layer 3 Compounds, disilylcarbazole, disilylbenzofuran, disilylbenzothiophene, disilylbenzophosphol, disilylbenzothiophene S-oxide and disilylbenzothiophene S,S-dioxide (e.g., It is possible to use disilyl compounds selected from the group consisting of WO2009/003919 and WO2009003898) and disilyl compounds (as disclosed in WO2008/034758).

Suitable electron conductor materials for layer (5) of the inventive OLED are metal chelated oxynoid compounds, such as 2,2',2"-(1,3,5-phenylene)tris[1-phenyl-1H- Benzimidazole] (TPBI), tris(8-quinolinolato)aluminum (Alq ₃ ), compounds based on phenanthrolines, such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrol Lean (DDPA = BCP) or 4,7-diphenyl-1,10-phenanthroline (DPA), and azole compounds such as 2-(4-biphenylyl)-5-(4-t-butylphenyl) -1,3,4-oxadiazole (PBD) and 3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ) , 8-hydroxyquinolinoleitolithium (Liq), 4,7-diphenyl-1,10-phenanthroline (BPhen), bis(2-methyl-8-quinolinolato)-4-(phenyl Phenolato) Aluminum (BAlq), 1,3-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]benzene (Bpy-OXD) , 6,6'-bis[5-(biphenyl-4-yl)-1,3,4-oxadiazo-2-yl]-2,2'-bipyridyl (BP-OXD-Bpy), 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), 2,9-bis(naphthalen-2-yl)-4,7-diphenyl -1,10-phenanthroline (NBphen), 2,7-bis[2-(2,2'-bipyridin-6-yl)-1,3,4-oxadiazo-5-yl]-9 ,9-dimethylfluorene (Bby-FOXD), 1,3-bis[2-(4-tert-butylphenyl)-1,3,4-oxadiazo-5-yl]benzene (OXD-7), Tris(2,4,6-trimethyl-3-(pyridin-3-yl)phenyl)borane (3TPYMB), 1-methyl-2-(4-(naphthalen-2-yl)phenyl)-1H-imidazo[ 4,5-f][1,10]phenanthroline (2-NPIP), 2-phenyl-9,10-di(naphthalen-2-yl)anthracene (PADN), 2-(naphthalen-2-yl) -4,7-diphenyl-1,10-phenanthroline (HNBphen) Layer (5) is a buffer layer to facilitate electron transport and to prevent quenching of excitons at the interface of the layer of the OLED. Or as a barrier layer All can work. Layer 5 preferably improves the mobility of electrons and reduces the quenching of excitons. In a preferred embodiment, TPBI is used as the electron conductor material. In another preferred embodiment, BCP is used as the electron conductor material. In principle, it is possible for the electron conductor layer to contain at least one compound of formula (I) as the electron conductor material.

The electron-transport layer can also be electronically doped primarily to make the layer thickness more generous (pinhole/short circuit protection) and to minimize the operating voltage of the device, thereby improving the transport properties of the materials used. Electronic doping is known to those skilled in the art, see, eg, W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, number 1, 1 July 2003 (p-doped organic layer); AG Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo, Appl. Phys. Lett., Vol. 82, number 25, 23 June 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103 and K. Walzer, B. Maennig, M. Pfeiffer, K. Leo, Chem. Soc. Rev. 2007, 107, 1233. For example, it is possible to use mixtures that lead to electrical n-doping of the electron-transporting layer. n-doping is achieved by the addition of reducing materials. These mixtures are, for example, mixtures of the aforementioned electron transport materials with alkali metal/alkaline earth metals or alkali metal/alkaline earth metal salts, such as Li, Cs, Ca, Sr, Cs ₂ CO ₃ , alkali metal complexes , Mixtures with, for example, 8-hydroxyquinolatorium (Liq), and Y, Ce, Sm, Gd, Tb, Er, Tm, Yb, Li ₃ N, Rb ₂ CO ₃ , dipotassium from EP1786050 Phthalates, mixtures with W(hpp) ₄ , or mixtures with compounds described in EP1837926B1, EP1837927, EP2246862 and WO2010132236.

이 가장 바람직하다.It is likewise possible to use alkali metal hydroxyquinolate complexes, preferably mixtures of Liq and dibenzofuran compounds in the electron-transporting layer. See WO2011/157790. Dibenzofuran compounds A-1 to A-36 and B-1 to B-22 described in WO2011/157790 are preferred, where dibenzofuran compounds

This is most preferred.

In a preferred embodiment, the electron-transporting layer comprises Liq in an amount of 99 to 1% by weight, preferably 75 to 25% by weight, more preferably about 50% by weight, wherein the amount of Liq and the dibenzofuran compound The amount of compound(s), especially ETM-1, is 100% by weight in total.

의 피리딘 화합물이 특히 바람직하다.It is likewise possible to use alkali metal hydroxyquinolate complexes, preferably mixtures of Liq and pyridine compounds, in the electron-transporting layer. See WO2011/157779. Chemical formula

The pyridine compound of is particularly preferred.

의 화합물, US2012/0261654에 기재된 화합물, 예컨대 예를 들어 화학식

의 화합물, 및 WO2012/115034에 기재된 화합물, 예컨대 예를 들어 화학식

의 화합물을 포함한다.In a further preferred embodiment, the electron-transporting layer is a compound described in WO2012/111462, WO2012/147397, WO2012014621, for example, a formula

Of the compound, a compound described in US2012/0261654, such as, for example, the formula

And compounds described in WO2012/115034, such as, for example, the formula

Contains compounds of.

Among the above-mentioned materials as hole conductor materials and electron conductor materials, some can fulfill several functions. For example, some of the electron-conducting materials are also hole-blocking materials at the same time if they have a low-level HOMO. These can be used, for example, in the hole/excitation barrier layer 4. However, layer 4 may not be used, as it is also possible that the function as a hole/exciter blocker is also adopted by layer 5.

The charge transport layer can also be electronically doped primarily to make the layer thickness more generous (pinhole/short circuit protection) and to minimize the operating voltage of the device, thereby improving the transport properties of the materials used. For example, the hole conductor material can be doped with electron acceptors; For example, phthalocyanine or arylamine, such as TPD or TDTA, can be doped with tetrafluorotetracyanoquinomethane (F4-TCNQ) or with MoO ₃ or WO ₃ . The electron conductor material can be doped, for example, with an alkali metal, for example Alq ₃ containing lithium. In addition, the electron conductor can be doped with a salt, such as Cs ₂ CO ₃ , or 8-hydroxyquinolelithium (Liq). Electronic doping is known to those skilled in the art, see, eg, W. Gao, A. Kahn, J. Appl. Phys., Vol. 94, number 1, 1 July 2003 (p-doped organic layer); AG Werner, F. Li, K. Harada, M. Pfeiffer, T. Fritz, K. Leo. Appl. Phys. Lett., Vol. 82, number 25, 23 June 2003 and Pfeiffer et al., Organic Electronics 2003, 4, 89-103. For example, a hole conductor layer other than a carbene complex, for example Ir(dpbic) ₃ , can be doped with MoO ₃ or WO ₃ . For example, the electron conductor layer can include BCP doped with Cs ₂ CO ₃ .

The cathode 6 is an electrode that acts to introduce electrons or negative charge carriers. Suitable materials for the cathode are alkali metals of group Ia of the Periodic Table of Elements (old version of IUPAC), for example alkaline earth metals of group Li, Cs, IIa, such as calcium, barium or magnesium, metals of group IIb (lanthanide and actinide For example, samarium). It is also possible to use metals such as aluminum or indium, and combinations of all the metals mentioned. In addition, an alkali metal, in particular a lithium-comprising organometallic compound, or an alkali metal fluoride, such as, for example, LiF, CsF, or KF, can be applied between the organic layer and the cathode to reduce the operating voltage.

The OLED according to the invention may further comprise additional layers known to those skilled in the art. For example, a layer that facilitates the transport of positive charges and/or matches the band gap of the layers can be applied between the layer 2 and the light emitting layer 3. Alternatively, this additional layer can act as a protective layer. In a similar manner, additional layers may be present between the light emitting layer 3 and the layer 4 to facilitate the transport of negative charges and/or to match the band gaps between the layers. Alternatively, this layer can act as a protective layer.

In a preferred embodiment, the OLED of the invention comprises at least one of the following layers mentioned below in addition to layers (1) to (6):

A hole injection layer between the anode 1 and the hole transport layer 2, having a thickness of 2 to 100 nm, preferably 5 to 50 nm;

-An electron blocking layer between the hole-transport layer 2 and the light-emitting layer 3;

-An electron injection layer between the electron-transporting layer 5 and the cathode 6.

The material for the hole injection layer is copper phthalocyanine, 4,4',4"-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris( N-(2-naphthyl)-N-phenylamino)triphenylamine (2T-NATA), 4,4',4"-tris(N-(1-naphthyl)-N-phenylamino)triphenylamine (1T-NATA), 4,4',4"-tris(N,N-diphenylamino)triphenylamine (NATA), titanium phthalocyanine oxide, 2,3,5,6-tetrafluoro-7,7 ,8,8-tetracyanoquinodimethane (F4-TCNQ), pyrazino[2,3-f][1,10]phenanthroline-2,3-dicarbonitrile (PPDN), N,N, N',N'-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD), 2,7-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobiflu Orene (MeO-spiro-TPD), 2,2'-bis[N,N-bis(4-methoxyphenyl)amino]-9,9-spirobifluorene (2,2'-MeO-spiro-TPD ), N,N'-diphenyl-N,N'-di-[4-(N,N-ditolylamino)phenyl]benzidine (NTNPB), N,N'-diphenyl-N,N'-di -[4-(N,N-diphenylamino)phenyl]benzidine (NPNPB), N,N'-di(naphthalen-2-yl)-N,N'-diphenylbenzene-1,4-diamine (α -NPP). In principle, it is possible for the hole injection layer to contain at least one compound of formula (I) as a hole injection material. In addition, polymeric hole-injecting materials such as poly(N-vinylcarbazole) (PVK), polythiophene, polypyrrole, polyaniline, self-doped polymers such as, for example, sulfated poly(thiophene-3-[2 [(2-methoxyethoxy)ethoxy]-2,5-diyl) (Plexcore® OC conductive ink commercially available from Plextronics), and copolymers such as poly(3, 4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (also referred to as PEDOT/PSS) can be used.

Compounds of formula (I), especially compounds of formula (Ia), (Ib), (Ic), (Id), (Ie), (If), (Ii), (Ij), (Il) or (In) , Very particularly compounds A-1 to A-65, B-1 to B-8, C-1 to C-65, D-1 to D-8, E-1 to E-65, or F-1 to F -65 can be used as the electron/exciter blocker material.

Metal complexes suitable for use as electron/exciter blocker materials are, for example, carbene complexes as described in WO2005/019373A2, WO2006/056418A2, WO2005/113704, WO2007/115970, WO2007/115981 and WO2008/000727. One example of a suitable carbene complex is compound HTM-1.

As a material for the electron injection layer, LiF can be selected, for example. In principle, it is possible for the electron injection layer to contain at least one compound of formula (I) as the electron injection material.

The skilled artisan knows how to select suitable materials (eg, based on electrochemical research). Materials suitable for individual layers are known to the skilled person and are disclosed, for example, in WO 00/70655.

In addition, it is possible to increase the efficiency of charge carrier transport by surface-treating a part of the layer used in the OLED of the present invention. The choice of material for each layer mentioned is preferably determined by obtaining an OLED with high efficiency and lifetime.

The OLED of the present invention can be produced by methods known to those skilled in the art. In general, the OLEDs of the present invention are produced by continuous deposition of individual layers onto suitable substrates. Suitable substrates are, for example, glass, inorganic semiconductors or polymer films. For deposition, it is possible to use conventional techniques such as thermal evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD), and the like. In an alternative method, the organic layer of the OLED can be applied from a solution or dispersion in a suitable solvent using coating techniques known to those skilled in the art.

In general, the different layers have the following thickness: anode (1) 50 to 500 nm, preferably 100 to 200 nm; Hole-conductive layer (2) 5 to 100 nm, preferably 20 to 80 nm, luminescent layer (3) 1 to 100 nm, preferably 10 to 80 nm, hole/exciter blocking layer (4) 2 to 100 nm , Preferably 5 to 50 nm, electron-conducting layer (5) 5 to 100 nm, preferably 20 to 80 nm, cathode (6) 20 to 1000 nm, preferably 30 to 500 nm. The relative position of the recombination zones of holes and electrons in the OLED of the present invention in relation to the cathode and hence the emission spectrum of the OLED, among other factors, can be influenced by the relative thickness of each layer. This means that the thickness of the electron transport layer should preferably be selected so that the location of the recombination zone matches the optical resonator properties of the diode and thus the emission wavelength of the emitter. The ratio of the layer thickness of the individual layers in the OLED depends on the material used. The layer thickness of any additional layer used is known to those skilled in the art. It is possible that the electron-conducting layer and/or the hole-conducting layer have a thickness greater than the layer thickness specified when they are electrically doped.

The use of a compound of formula (I) in at least one layer of the OLED, preferably in the light emitting layer (preferably as a matrix material) and/or in the hole/exciter blocking layer, results in high efficiency and low use and operating voltage. Having the OLED makes it possible to obtain. Frequently, OLEDs obtained by the use of compounds of formula (I) have a further high lifetime. The efficiency of the OLED can be further improved by optimizing the other layers of the OLED. For example, high-efficiency cathodes, such as Ca or Ba, can be used in combination with an intermediate layer of LiF where appropriate. Molded substrates and novel hole-transport materials that cause a reduction in operating voltage or an increase in quantum efficiency are likewise usable in the inventive OLEDs. Moreover, additional layers may be present in the OLED to adjust the energy levels of the different layers and to facilitate electroluminescence.

The OLED may further include at least one second light emitting layer. The total emission of the OLED may consist of the emission of at least two emitting layers, and may also include white light.

OLEDs can be used in any device where electroluminescence is useful. Suitable devices are preferably selected from fixed and mobile visual display devices and lighting devices. Stationary visual display devices are, for example, visual display devices for computers, televisions, printers, kitchen utensils and advertising panels, and visual display devices in lighting and guidance panels. The mobile visual display device is, for example, a visual display device in a mobile phone, a tablet PC, a portable computer, a digital camera, an MP3 player, a vehicle, and a destination display of buses and trains. Additional devices in which the OLED of the present invention can be used include, for example, a keyboard; Clothing items; furniture; It is wallpaper. In addition, the present invention includes at least one organic light emitting diode of the present invention or at least one light emitting layer of the present invention, a fixed visual display device, such as a computer, television visual display device, printers, kitchen appliances and billboards, lighting, A visual display device in a guide plate, and a mobile visual display device, such as a mobile phone, a tablet PC, a portable computer, a digital camera, an MP3 player, a visual display device in vehicles and destination displays of buses and trains; Lighting devices; keyboard; Clothing items; furniture; It relates to a device selected from the group consisting of wallpaper.

The following examples are included for illustrative purposes only and do not limit the scope of the claims. All parts and percentages are by weight, unless stated otherwise.

Example

Example 1

a) 20.0 g (78.8 mmol) of 1,3-dibromo-5-fluoro-benzene in 200 ml DMF, 16.3 g (78.8 mmol) of 6H-benzimidazolo[1,2-a]benzimidazole and Potassium carbonate 43.5 g (0.315 mmol) was stirred at 170° C. for 17 hours. The reaction mixture was filtered hot, and the precipitate from the mother liquor was filtered after cooling. The product was washed with water and ethanol and decanted with diethyl ether and ethanol. Yield 21.2 g (61%).

b) 3.31 g (7.5 mmol) of the product of Example 1a), 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane -2-yl) A mixture of 4.76 g (18.75 mmol) of 1,3,2-dioxaborolane and 5.89 g (60 mmol) of potassium acetate was evacuated and flushed 5 times with argon. 40 ml of DMF was added, the mixture was evacuated and flushed. 428.7 mg (0.525 mmol) of 1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II) was added under argon. The reaction mixture was heated to 65° C., stirred for 3.5 hours, then cooled to room temperature, and the solvent was removed under reduced pressure. The residue was dissolved in 120 ml water and 120 ml tert-butyl methyl ether (TBME), stirred for several minutes and filtered. The phases were separated and the H ₂ O phase was extracted with TBME. The organic phase was dried, evaporated and stirred with 50 ml of hot isopropanol for 15 minutes. The suspension was filtered, and the residue was washed with isopropanol and dried to give 2.29 g. The filtrate was evaporated and crystallized in isopropanol to give 319 mg. Total yield: 2.61 g (65%).

c) Literature [T. Jensen in Angew. Chem. Int. Ed. 47 (2008) 888, similar to the procedure described in 3-chloro-4-iodo-pyridine was prepared starting from 3-chloro-pyridine (yield: 52.9%).

d) 3-chloro-4-iodo-pyridine 11.1 g (46.35 mmol), 5-bromo-2-methoxy-phenylboronic acid 10.17 g (44.03 mmol), potassium carbonate 32.67 g (236.39 mmol), toluene 350 ml, ethanol 160 ml and water 88 ml were mixed, vented and flushed with argon 4 times. Then, 2.68 g (2.31 mmol) of tetrakis triphenyl phosphine palladium was added, vented again, and flushed with argon 4 times. The resulting transparent mixture was heated to reflux for 3 hours with stirring, then cooled to room temperature. The phases were separated and the aqueous phase was extracted twice with toluene (200 ml each). The combined organic phase was washed 3 times with water (100 ml each), dried over magnesium sulfate, filtered and the solvent was evaporated on a rotary evaporator. The crude product (16.07 g) was purified by flash column chromatography using hexane/ethyl acetate as eluent to give 10.94 g (83.2%) of 4-(4-bromo-2-methoxy-phenyl)-3-chloro-pyridine. ) As a colorless oil, which solidified upon standing.

e) 10.94 g (36.64 mmol) of 4-(4-bromo-2-methoxy-phenyl)-3-chloro-pyridine was dissolved in 200 ml of anhydrous dichloromethane. Within 20 minutes, 145.9 ml (145.9 mmol) of a 1M boron tribromide solution in dichloromethane was added using a syringe while maintaining the temperature at room temperature using a water bath. The cooling was removed and the solution was stirred at room temperature for 18 hours. Then, 500 ml of water was added dropwise. An exothermic reaction occurred and the mixture began to reflux. The mixture was stirred for 30 minutes, then added to 200 ml of buffer (pH = 7). 2N NaOH solution was added until pH 7 was reached. Then, 500 ml of ethyl acetate was added. The phases were separated and the aqueous phase was extracted twice with ethyl acetate (250 ml each). The combined organic phase was washed 3 times with water (100 ml each), dried over magnesium sulfate, filtered and the solvent was evaporated on a rotary evaporator to a volume of 100 ml. The suspension was cooled to 0° C. using an ice bath, filtered and the residue washed three times with ice cold ethyl acetate (5 ml each). The product was dried overnight at 50°C/125 mbar to give 8.99 g (86.2%) of 5-bromo-2-(3-chloro-4-pyridyl)phenol.

f) [J. Org. Chem. Similar to the procedure described in 73 (7) 2951 (2008) (J. Liu)], 5-bromo-2-(3-chloro using copper(I)-thiophene-2-carboxylate (CuTC). 7.85 g (27.59 mmol) of -4-pyridyl)phenol are cyclized with 6-bromo-4a,4b,8a,9a-tetrahydrobenzofuro[2,3-c]pyridine and hexane/ethyl acetate as eluent 54.1% yield was obtained after flash chromatography using 2:1.

g) A mixture of 401.4 mg (0.75 mmol) of the product of Example 1b) and 465.1 mg (1.875 mmol) of the product of Example 1f was evacuated and flushed three times with argon. Tetrahydrofuran 6 ml (THF) was added. 955.2 mg (4.5 mmol) of K ₃ PO ₄ and 25 ml of water were bubbled with argon in a separate flask for 25 minutes. Tris t-butylphosphonium tetrafluoroborate 13.1 mg (0.045 mmol) and Pd ₂ (dba) ₃ 20.6 mg (0.023 mmol) were added to the mixture of starting materials in THF, bubbling with argon for 3 minutes, Heated to 50°C. The K ₃ PO ₄ solution was added at once using a syringe, and the reaction mixture was heated at a bath temperature of 75° C. for 4 hours. The reaction mixture was cooled to room temperature, and 20 ml of water was added. The THF was evaporated, the reaction mixture was filtered, and the residue was washed with water and methanol and dried. The crude product was stirred in CHCl ₃ 100 ml for 30 minutes, filtered through hyflo (Hyflo) and washed with CHCl _3. The filtrate was evaporated, then stirred in 8 ml of hot CHCl ₃ , filtered, and the residue was washed with CHCl ₃ and dried. Yield: 407.6 mg (88%)

Example 2

a) 1-bromo-3-iodo-benzene 7.78 g (25.0 mmol), cesium carbonate 16.3 g (50.0 mmol), copper iodide (I) 1.24 g (6.50 mmol) and L-proline 1.50 g (13.0) mmol) was added under nitrogen to 5.18 g (25.0 mmol) of 5H-benzimidazole[1,2-a]benzimidazole in 100 ml dimethyl sulfoxide (DMSO). The reaction mixture was stirred at 100° C. for 18 hours, then poured into water. The aqueous phase was extracted with dichloromethane and dried over magnesium sulfate. The solvent was distilled off. Column chromatography on silica gel with toluene gave the product in a yield of 8.35 g (92%).

b) 1.0 g (2.73 mmol) of the product of Example 2a), 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane -2-yl)-1,3,2-dioxaborolan 831.2 mg (3.27 mmol), potassium acetate 1.61 g (16 mmol) and 25 ml of DMF were evacuated and flushed 5 times with argon. 111.4 mg (0.136 mmol) of 1,1'-bis(diphenylphosphino)ferrocene)dichloropalladium(II) was added, the reaction mixture was evacuated and flushed 5 times with argon. The reaction mixture was stirred at 60° C. for 20 hours, cooled to room temperature, and then evaporated under reduced pressure. 50 ml of water, 50 ml of TBME and 3 ml of a solution of 1% NaCN in water were added, and the mixture was stirred for 30 minutes, filtered and washed with 100 ml of ethyl acetate. The phases were separated, the aqueous phase was extracted with ethyl acetate, and the organic phase was dried and evaporated. Yield: 0.8 g (72%)

c) 13.92 g (46.56 mmol) of 2-amino-3-iodo-5-bromopyridine, 11.71 g (50.75 mmol) of 5-bromo-2-methoxy-phenylboronic acid, 32.82 g of potassium carbonate (237.44 mmol) ), 700 ml of toluene, 280 ml of ethanol and 175 ml of water were mixed, vented and flushed 4 times with argon. Then, 5.38 g (4.66 mmol) of tetrakis triphenyl phosphine palladium was added. The mixture was heated to reflux for 2.5 hours with stirring, then cooled to room temperature. The phases were separated and the aqueous phase was extracted twice with toluene (250 ml each). The combined organic phase was washed 3 times with water (100 ml each), dried over magnesium sulfate, filtered and the solvent was evaporated on a rotary evaporator. The crude product (16.8 g) was purified by flash chromatography using heptane/ethyl acetate as eluent to 12.4 g 5-bromo-3-(5-bromo-2-methoxyphenyl)pyridin-2-amine ( 74%).

d) A solution of 12.4 g (35 mmol) of 5-bromo-3-(5-bromo-2-methoxyphenyl)pyridin-2-amine in 170 ml THF and 430 ml glacial acetic acid was cooled to 0° C., tert -Butyl nitrite 7.14 g (69 mmol) was added dropwise. The reaction mixture was stirred overnight at 0° C., warmed to room temperature, poured into 800 ml of ice water and stirred for 1 hour. The yellow suspension was filtered, washed with ice water and dried to give 8.5 g (75%) of pure product.

e) 267.3 mg (0.818 mmol) of the product of Example 2d), 702.7 mg (1.72 mmol) of the product of Example 2b), 576.2 mg (4.17 mmol) of K ₂ CO ₃ , 50 ml of toluene, 25 ml of ethanol and 11 ml of water The mixture of was evacuated and flushed 5 times with argon. Tetrakis triphenyl phosphine palladium 47.2 mg (0.041 mmol) was added and the reaction mixture was heated to reflux for 18 hours. 10 ml of a 2% solution of NaCN in water was added and the reaction mixture was cooled to room temperature. 50 ml of water and 50 ml of toluene were added, and the suspension was stirred for 15 minutes, filtered, washed with toluene/water and dried. Yield: 330 mg (55%) of yellow crystals.

Application Example 1

The ITO substrate used as the anode was first cleaned with an acetone/isopropanol mixture in an ultrasonic bath. To remove any possible organic residues, the substrate was exposed to a continuous ozone flow in an ozone oven for an additional 25 minutes. This treatment also improved the hole injection properties of ITO. The FlexCore® OC AJ20-1000 (commercially available from Flextronics Inc.) was then spin-coated and dried to form a hole injection layer (~40 nm).

을 20 nm의 두께로 기판에 적용하였으며, 여기서 처음 10 nm를 MoO_x (~10%)로 도핑하여 전도성을 개선하였다.It was applied to the clean substrate by evaporation to approximately 0.5-5 nm / min at 10 ^-9 mbar - and then, to the specified organic material of about ^10-7. As a hole transport and exciton blocker,

Was applied to the substrate with a thickness of 20 nm, where the first 10 nm was doped with MoO _x (~10%) to improve conductivity.

10 중량% 및 화합물

90 중량%의 혼합물을 40 nm의 두께로 증착에 의해 적용하였다. 이어서, 화합물 (E-57)을 차단제로서 5 nm 두께로 증착시켰다. 그 후에,

50 중량% 및

50%로 이루어진 20 nm 두께의 전자 수송 층을 증착시켰다. 최종적으로 2 nm KF 층이 전자 주입 층으로서 작용하였으며, 100 nm-두께의 Al 전극으로 장치가 완성되었다.Subsequently, the emitter compound

10% by weight and compound

90% by weight of the mixture was applied by vapor deposition to a thickness of 40 nm. Subsequently, compound (E-57) was deposited as a blocking agent to a thickness of 5 nm. After that,

50% by weight and

A 20 nm thick electron transport layer of 50% was deposited. Finally, a 2 nm KF layer served as the electron injection layer, and the device was completed with a 100 nm-thick Al electrode.

All manufactured parts were sealed with a glass lid and getter under an inert nitrogen atmosphere.

To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristics were measured along with the emitted light output. By calibrating the light output with a photometer, it was possible to convert to photometric parameters.

¹⁾ External quantum efficiency (EQE) is # of generated photons emitted from a substance or device / # of electrons flowing through it.

Application Example 2

92 중량% 및 화합물

8 중량%를 약 10^-7 -10^-9 mbar에서 대략 0.5-5 nm/분의 속도로 증착에 의해 80 nm의 두께로 석영 기판에 적용하였다.compound

92% by weight and compound

8% by weight was applied to the quartz substrate to a thickness of 80 nm by deposition at a rate of approximately 0.5-5 nm/min at about 10 ^-7 -10 ^-9 mbar.

PL spectra and PL quantum efficiency were measured at room temperature using an absolute quantum-yield measurement system “Quantaurus” (Hamamatsu, Japan) at an excitation wavelength of 370 nm.

Claims (15)

A compound of formula (II):

(II)
In the above formula,
B ¹ is N or CR ⁸¹ ,
B ² is N or CR ⁸² ,
B ³ is N or CR ⁸³ ,
B ⁴ is N or CR ⁸⁴ ,
B ⁵ is N or CR ⁸⁵ ,
B ⁶ is N or CR ⁸⁶ ,
B ⁷ is N or CR ⁸⁷ ,
B ⁸ is N or CR ⁸⁸ , wherein R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ independently of each other can be substituted by H, optionally E and/or D C ₁ -C ₂₅ alkyl group which may be interposed; A C ₆ -C ₂₄ aryl group optionally substituted by G, a C ₂ -C ₃₀ heteroaryl group optionally substituted by G; Formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -R ¹⁶ or -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) a group of _r -X ¹ ,
o is 0 or 1, p is 0 or 1, q is 0 or 1, r is 0 or 1,
A ¹ , A ² , A ³ and A ⁴ are independently of each other a C ₆ -C ₂₄ arylene group which may be optionally substituted by G, or a C ₂ -C ₃₀ heteroarylene group which may be optionally substituted by G ego;
R ¹⁶ is —NR ¹⁰ R ¹¹ , or —Si(R ¹² )(R ¹³ )(R ¹⁴ ), a C ₆ -C ₂₄ aryl group which may be optionally substituted by G; Or a C ₂ -C ₃₀ heteroaryl group which may be optionally substituted by G;
R ¹⁰ and R ¹¹ are independently of each other a C ₆ -C ₂₄ aryl group which may be optionally substituted by G; Or a C ₂ -C ₃₀ heteroaryl group which may be optionally substituted by G;
R ¹² , R ¹³ and R ¹⁴ are independently of each other a C ₁ -C ₂₅ alkyl group which may be optionally substituted by E and/or may be interrupted by D; A C ₆ -C ₂₄ aryl group which may be optionally substituted by G; Or a C ₂ -C ₃₀ heteroaryl group which may be optionally substituted by G;
D is -CO-, -COO-, -S-, -SO-, -SO ₂ -, -O-, -NR ⁶⁵ -, -SiR ⁷⁰ R ⁷¹ -, -POR ⁷² -, -CR ⁶³ =CR ⁶⁴ -Or -C≡C-,
E is -OR ⁶⁹ , -SR ⁶⁹ , -NR ⁶⁵ R ⁶⁶ , -COR ⁶⁸ , -COOR ⁶⁷ , -CONR ⁶⁵ R ⁶⁶ , -CN or F,
G is E, or C ₁ -C ₁₈ alkyl group, a C ₆ -C ₂₄ aryl group, or F, C ₁ a C ₆ -C ₂₄ substituted with a -C ₁₈ alkyl or C ₁ -C ₁₈ alkyl, O is interposed Aryl group; C ₂ -C ₃₀ heteroaryl group, or F, C ₁ -C ₁₈ alkyl or O is interposed a C ₁ a C ₂ -C ₃₀ heteroaryl group is substituted by -C ₁₈ alkyl;
R ⁶³ and R ⁶⁴ are independently of each other H, C ₆ -C ₁₈ aryl; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl; Or C ₁ -C ₁₈ alkyl interrupted by -O-;
R ⁶⁵ and R ⁶⁶ are independently of each other a C ₆ -C ₁₈ aryl group; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-; or
R ⁶⁵ and R ⁶⁶ together form a 5 or 6 membered ring,
R ⁶⁷ is a C ₆ -C ₁₈ aryl group; A C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-,
R ⁶⁸ is H; C ₆ -C ₁₈ aryl group; A C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-,
R ⁶⁹ is C ₆ -C ₁₈ aryl; C ₆ -C ₁₈ aryl substituted by C ₁ -C ₁₈ alkyl or C ₁ -C ₁₈ alkoxy; C ₁ -C ₁₈ alkyl group; Or a C ₁ -C ₁₈ alkyl group interrupted by -O-,
R ⁷⁰ and R ⁷¹ are independently of each other a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₁₈ aryl group, or a C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl,
R ⁷² is a C ₁ -C ₁₈ alkyl group, C ₆ -C ₁₈ aryl group, or C ₆ -C ₁₈ aryl group substituted by C ₁ -C ₁₈ alkyl,
At least one of the substituents R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ and R ⁸⁸ is of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -( A ⁴ ) _r -X ¹ ; here
X ¹ is Cl, Br or I, ZnX ¹² (X ¹² is a halogen atom); -SnR ²⁰⁷ R ²⁰⁸ R ²⁰⁹ (where R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ are the same or different, H or C ₁ -C ₈ alkyl, where the two radicals optionally form a common ring, and these radicals are Optionally branched or unbranched); -B(OH) ₂ , -B(OY ¹ ) ₂ ,

, -BF ₄ Na or -BF ₄ K (where Y ¹ is independently a C ₁ -C ₁₈ alkyl group in each case, Y ² is a C ₂ -C ₁₀ alkylene group independently in each case, Y ¹³ and Y ¹⁴ are independently of each other hydrogen or a C ₁ -C ₁₈ alkyl group), except for the following compounds:

. The compound of claim 1, wherein X ¹ is Cl, Br, or I, p is 0, q is 0 and r is 0. According to claim ¹ , X ¹ Is -B (OH) ₂ , -B (OY ¹ ) ₂ ,

or

Phosphorus compound. The compound according to claim 1 of the formula:

. The substituents R ⁸¹ , R ⁸² , R ⁸³ , R in compounds of the formulas (II'), (II"), (II"'), (II"") and (II""') ^{One of 85} , R ⁸⁶ and R ⁸⁷ is a compound of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -X ¹ . The substituents R ⁸¹ , R ⁸² , R ⁸³ , R in compounds of the formulas (II'), (II"), (II"'), (II"") and (II""') Two of ⁸⁵ , R ⁸⁶ and R ⁸⁷ are compounds of the formula -(A ¹ ) _o -(A ² ) _p -(A ³ ) _q -(A ⁴ ) _r -X ¹ . The compound according to claim 1 of the formula:

8. Compounds of formula (IIa), (IIb), (IIc), (IId), (IIe), (IIf), (IIi), (IIj), (IIl) or (IIn) according to claim 7. An electronic device comprising the compound according to claim 1. The electronic device according to claim 9, which is an electroluminescent device. A fixed visual display device comprising the organic electronic device according to claim 9 or 10; A mobile visual display device; Lighting devices; keyboard; Clothing items; furniture; A device selected from the group consisting of wallpaper. An electrophotographic photoreceptor comprising the compound according to any one of claims 1 to 8, a photoelectric converter, an organic solar cell, a switching element, an organic light emitting field effect transistor, an image sensor, a dye laser and an electroluminescent device. Device selected from the group. A compound of formula (Ia):

In the above formula,
R ^{83 teeth}

or

Is the flag of
R ⁸⁷ is H,

Group, or formula

Compound of the formula (Ia), which is a group of. An electronic device comprising the compound according to claim 13. The electronic device according to claim 14, which is an electroluminescent device.