DE10038436A1 - New 5-acceptor-functionalized 2-diarylamino thiophene or thiazole derivatives, especially useful for making organic light-emitting diodes - Google Patents

Abstract

5-Acceptor-functionalized 2-diarylamino thiophene or thiazole derivatives (I) are new. 5-Acceptor-functionalized 2-diarylamino thiophene or thiazole derivatives of formula (I) are new. Q = a group of formula Q1-Q3; R<1> = aryl or heteroaryl optionally substituted by 1-6C alkyl, 1-6C alkoxy, phenoxy, di(1-6C alkyl)amino or diphenylamino, or arylene or heteroarylene optionally substituted by 1-6C alkyl, 1-6C alkoxy, phenoxy, di(1-6C alkyl)amino or diphenylamino; R<2> = aryl or heteroaryl optionally substituted by 1-6C alkyl, 1-6C alkoxy, phenoxy, di(1-6C alkyl)amino or diphenylamino; R<3> = H or R<2>; X = N or CR<8>; R<8> = H or R<2>; R<4>, R<5> = nitrile, carboxylate ester or carboxamide groups, trityl or R<2>, or together form a cyclic ureide or thioureide group, where the ester, amide and ureide groups may comprise 1-10C alkyl groups; Y = C or N, where other aromatic ring structures can be fused at bonds c, d and e when Y is C or at bond d when Y is N; provided that R<3> is H when Q is (Q2) or (Q3). Independent claims are also included for the following: (1) Polymers of compounds (I). (2) Processes for preparing compounds (I). (3) Processes for producing organic light-emitting diodes in which the light-emitting layer is produced by vapor deposition or spin coating with compounds (I) or their polymers.

Description

The invention relates to chromophores with semiconducting properties as well as their manufacture and their application as Lumi nophores in organic light emitting diodes (OLEDS).

In recent years, many organic materials have been in Researched on their electronic properties wor the. In addition to connections with extensive π electron systems In particular, connections that have a high glass prove themselves have transition temperature and therefore not or only very difficult to crystallize. That is why polymers are too large ten π electron systems, such as. B. Poly (p-phenylene) PPP and Poly (p-phenylene vinylene) PPV as light-emitting polymers have been introduced (cf. G. Gustafsson et al in "Nature" Volume 357, 1992 pp. 477 ff).

For covering the long-wave emitting spectral range ches (orange to red) are these connection classes only limits suitable, since they usually emit shorter-wave. Especially for the OLEDS based on so-called "Small Molecules "(e.g. US Pat. No. 4,539,507) are long-wave emitting luminophores can only be used to a very limited extent as these due to their larger π systems and inevitable struk tural planarity do not form glass-like phases and therefore crystallize very well. Such a luminophore has often a very high fluorescence quantum yield in solution, but with increasing concentration due to the association ation of the dye molecules to stack less and less is usually completely lost in the solid state. The associations tendency results from the usually extreme planarity of the Dye molecules.  

To be able to use such materials anyway, you can use them use only as a dopand, d. H. with a suitable glasarti Mix the phase-forming electron transport material (er testify to a solid solution) that thereby the fluorescence ability remains and no crystallization of the Chromophors in the non-crystallizing matrix used entry.

This, primarily with a long-wave emitting material problems occurring (little or no fluorescence solidity and crystallization) are new en amorphous luminophores according to the invention eliminated. Therefore Such electroluminescent layers can also be the same are used early as electron transport layers.

The object of the invention is to create new organic, amorphous, long to create wavy electroluminescent compounds that in organic light emitting diodes and / or in electronic construction elements can be used that are easily accessible and easy to process in mass production processes are.

The invention relates to compounds of types IV, VII and VIII

where the following applies:
R ¹ , R ² and R ³ are - independently of one another - each a monofunctional (het) aryl system, i.e. a conjugated carbocyclic or heterocyclic ring system, which can also consist of linear or angularly fused or linked identical or different ring types, the peripheral hydrogen atoms can optionally be substituted by alkyl, alkoxy, phenoxy, dialkylamino or diphenylamino groups (alkyl = C ₁ to C ₆ );
R ¹ can also be a corresponding bifunctional (het) aryl lens system, ie a conjugated carbocyclic or heterocyclic ring system which can also consist of linearly or angularly fused or linked identical or different ring types, the peripheral hydrogen atoms being optionally substituted by alkyl, alkoxy , Phenoxy, di alkylamino or diphenylamino groups (alkyl = C ₁ to C ₆ ) may be substituted;
X, which has the meanings -N = and -CR ⁸ =, where R ^{8 has} the meaning of R ² or hydrogen.

R ⁴ and R ⁵ , which can be the same or different, but represent a multiple or more complex group with electron acceptor character, which together with the C atom connecting both substituents are all derived from malonic acid and its cyclic ureide and thioureide Can understand groupings; Accordingly, R ⁴ and R ^{5 can be} nitrile groups, carboxylic acid ester groups, and carboxylic acid reamide groups, where the ester, amide or ureide residues can include branched or unbranched alkyl residues with up to 10 carbon atoms, triphenylmethyl residues (trityl residues) and R ² could be.

Y can be carbon or nitrogen. In case that Y = C can independently on the bonds c, d and e further aromatic ring structures are fused; For in the event that Y = N, further aroma can be found on the bond d table ring structures are fused.

The invention furthermore relates to a process for the preparation position of the compounds of types IV, VII and VIII.

Finally, the invention relates to the use of Compounds of types IV, VII and VIII in organic LEDs.

The new compounds according to the invention are preparative easily accessible and all derive from a Baukas system (see reaction scheme) of N, N-disubstituted Thiocarboxamides or N, N-disubstituted thiourea fen I off. They are part of mass production processes easy to process. In particular, it has been found that the connections, although they are basically "small molecules" are not only processable by evaporation, but also like polymers through spin coating. This makes it easier the economic usability of the compounds, also in With regard to the production of OLEDs (organic light emitting diodes).  

scheme

wherein all symbols have the meaning given above and R ⁶ and R ^{7 are} C ₄ - to C ₁₀ -alkyl groups or together a C ₉ - to C ₆ -alkylene group or a group -CH ₂ - CH ₂ -O-CH ₂ -CH ₂ - form.

Starting from a thiocarboxamide or thiourea I are the electroluminescent luminophores that are 5-acceptors functionalized 2-N, N-diarylaminothiophenes or -thiazoles IV on the steps of 2-N, N-diarylaminothiophenes or -thia zole II and 5-formyl-2-N, N-diarylamino-thiophene or -thiazole III accessible. The conversion of compound I to  Compound II takes place by means of ω-haloacylarenes through a Hantzsch analog reaction, the conversion of the compounds II to III using dimethylformamide and acid chloride according to the known Vilsmeier reaction and the conversion of the verbin dung III to IV with a malonic acid derivative by a con densation.

To prepare 2,3-dihetarylquinoxalines VII, the compounds of type I are first converted into correspondingly substituted 3-amino-thioacrylic acid amides or their 2-aza-analogous derivatives V by reaction in orthoformic acid ester and a preferably higher-boiling secondary amine (as " higher boiling "is an amine with a boiling point of at least 100 ° C). The compounds of type V are condensed in the presence of 1,4-dibromobutane-2,3-dione to give corresponding hetaryl benzene derivatives VI by S-alkylation and subsequent ring closure and aromatization. The hetarylbenzil derivatives VI are finally converted to the structure type of the new electro-luminescent chromophores VII using ortho-diaminoarylene derivatives. In the event that in the compounds of types VI and VII R ^{1 is} a bifunctional structure, these compounds are fundamentally polymeric.

From the compounds of type V, the likewise new electroluminescent chromophores, the 1,1-bishetaryl-2,2-bis-acceptor-substituted ethylene VIII, are obtained by reaction with 2,2-bishalomethylvinylidene malonic acid derivatives. Compound VIII is also polymeric if R ^{1 is} a bifunctional structure.

The amorphicity of the new chromophores improves in principle with an increase in the degree of aryl substitution on the hete roaromatic basic bodies.

The compounds IV, VII and VIII are not only suitable for use in OLEDs but also in electronic or microelectronic  Components, where solar cells or photo refractive components are mentioned as examples.

embodiments Type II compounds a) 2- (N, N-Diphenylamino) -4-phenylthiazole-1,3 IIa

In a 1 l flask with reflux condenser, heater and stirrer 99.5 g (= 0.5 mol) ω-bromo-acetophenone together with 114 g (= 0.5 mol) N, N-diphenylthiourea (Ia) and 250 ml of ethanol heated at reflux for 5 h. After the reaction has ended, the mixture is cooled and then pour the reaction mixture into with stirring 500 g ice cream. It is suctioned off from the aqueous phase and on finally the crude product is recrystallized from ethanol. The yield is 83%. Mp = 120 ° C

b) 2- (N, N-diphenylamino) -3,4-diphenylthiophene IIb

In a 1 l flask with reflux condenser, heater and stirrer 99.5 g (= 0.5 mol) ω-bromo-acetophenone together with 151 g (= 0.5 mol) 2-phenylthioacetic acid (N, N-diphenyl) amide (Ib) and refluxed 250 ml of ethanol for 5 h. After finished The reaction is cooled and then the reaction mixture is poured with stirring in 500 g of ice. It will depend on the aqueous phase sucked and then the raw product from ethanol crystallized. The yield is 80%. Mp = 105 ° C

Type III compounds a) 2- (N, N-Diphenylamino) -4-phenyl-5-formyl-thiazole-1,3 IIIa

4.2 g (= 0.0128 mol) of 2- (N, N-diphenylamino) -4-phenylthiazole-1,3 (IIa) are dissolved in 25 ml of dimethylformamide in a 250 ml beaker with a stirrer. While cooling to about 5 ° C., 3 g (= 0.02 mol) of phosphorus oxychloride POCl _{3 are} then slowly added, then the mixture is stirred for a further 30 minutes and heated to about 30 ° C. When the reaction has ended, the mixture is carefully poured into ice water, yellow crystals precipitating out. The crude product is filtered off and recrystallized from ethanol. The yield is 60%. Mp = 165 ° C

b) 2- (N, N-diphenylamino) -3,4-diphenyl-5-formylthiophene IIIb

6 g (= 0.015 mol) of 2- (N, N-diphenylamino) -3,4-diphenylthiophene (IIb) are dissolved in 25 ml of dimethylformamide in a 250 ml beaker with a stirrer. While cooling to about 5 ° C., 3.5 g (= 0.023 mol) of phosphorus oxychloride POCl ₃ are then slowly added, then the mixture is left to stir for a further 30 minutes and heated to about 30 ° C. After the reaction is poured carefully into ice water, whereby yellow crystals fall out. The crude product is filtered off and recrystallized from ethanol. The yield is 62%. Mp = 116 ° C

Type IV compounds aa) 1- [2- (N, N-diphenylamino) -4-phenylthiazol- (1,3) -5-yl] - 2,2-dicyanoethylene IVa

10 g of malononitrile are placed in a 250 ml beaker melted. In addition there are 1.78 g (= 0.005 mol) of 2- (N, N-diphenyl) amino) -4-phenyl-5-formyl-thiazole-1,3 (IIIa) and 2 ml of perchlor acid. The mixture is then stirred at about 70 ° C. for 15 minutes. After finished The reaction is taken up in a little ethanol and in 100 g of ice stirred in, the crude product is obtained. It is from the aqueous phase and crystallized twice from ethanol lisiert. The yield is 37%. Mp = 130-135 ° C.  

ab) 5- [5- (Diphenylamino) -3-phenyl-1,3-thiazol-2-yl] - methylene-1,3-diphenyl-2-thioxodihydro-4,6 (1H, 5H) - pyrimidinedione IVb

In a beaker, 0.01 mol of 2- (N, N-diphenylamino) -4- phenyl-5-formyl-thiazole-1,3 (IIIa) and 0.01 mol N, N-diphenyl thiobarbituric acid suspended in 40 ml acetic anhydride and under Stir until heated to boiling. After reaching the boiling point rature is allowed to cool on the hot plate. The product will suction filtered, washed with ethanol and ether and dried. Yield is 76%. Mp: 384 ° C.

ba) 1- [2- (N, N-diphenylamino) -3,4-diphenylthiophene-5-yl] -2,2- dicyanoethylene IVc

10 g of malononitrile are placed in a 250 ml beaker melted. In addition there are 1.72 g (= 0.004 mol) of 2- (N, N-diphenyl) amino) -3,4-diphenyl-5-formyl-thiophene (IIIb) and 2 ml Perch lorsäure. The mixture is then stirred at about 70 ° C. for 15 minutes. After been The reaction is taken up in a little ethanol and in 100 g Ice is stirred in, the crude product being obtained. It is from the aqueous phase and crystallized twice from ethanol lisiert. The yield is 33%. Mp = 290 ° C

bb) 5- [5- (Diphenylamino) -3,4-diphenyl-2-thienyl] -methylene- 1,3-diphenyl-2-thioxodihydro-4,6 (1H, 5H) pyrimidinediones IVd

In a beaker, 0.01 mol of 2- (N, N-diphenylamino) - 3,4-diphenyl-5-formyl-thiophene (IIIb) and 0.01 mol N, N- Diphenyl-thiobarbituric acid suspended in 40 ml acetic anhydride and heated to boiling with stirring. After reaching the Boiling temperature is allowed to cool on the hot plate. The The product is filtered off, washed with ethanol and ether and dried. Yield is 72%. Mp: 305 ° C.  

bc) bis-5- [5- (N, N'-diphenyl-4,4'-dibiphenylenamino) -3,4- diphenyl-2-thienyl] -methylene-1,3-diphenyl-2-thioxodihydro- 4,6 (1H, 5H) pyrimidinediones IVe

0.01 mol of 2- (N, N-diphenyl-4,4- dibiphenylenamino) -3,4-diphenyl-5-formyl-thiophene (type III) and 0.02 mol of N, N-diphenyl-thiobarbituric acid in 60 ml of acetane suspended hydride and heated to boiling with stirring. After the boiling temperature has been reached, the mixture is left on the heating plate cool down. The product is suctioned off, with ethanol and E. ther washed and dried. Yield is 80%. fp: 346 ° C.

Type V compounds a) 3-Morpholino-2-aza-thioarylic acid diphenylamide Va

In a 0.51 flask with a reflux condenser, heating device and 34.2 g (= 0.15 mol) of N, N-diphenylthiourea are stirred (Ia) together with 52.2 g (= 0.6 mol) morpholine and 88.8 g (= 0.6 mol) triethyl orthoformate for 7 h at 125 ° C warms. After the reaction is allowed to cool and ver thins with methanol. After a while, yellow crystals fall from which are suctioned off. The crude product is converted into ethanol crystallized. The yield is 73%. Mp = 238 ° C

b) 3-morpholino-2-phenylthioacrylic acid diphenylamide Vb

In a 0.5 l flask with a reflux condenser, heating device and 45.5 g (= 0.15 mol) of 2-phenylthioacetic acid are stirred diphenylamide (Ib) together with 52.2 g (= 0.6 mol) morpholine and 88.8 g (= 0.6 mol) of triethyl orthoformate for 7 h Heated to 125 ° C. After the reaction is allowed to cool and diluted with methanol. After a while, yellow crystals fall  from which are suctioned off. The raw product is in Etha nol recrystallized. The yield is 68%. Mp = 182 ° C

Type VI compounds a) 1,2-Di- (5-diphenylamino-1,3-thiazol-2-yl) ethanedione VIa

In a flask with a reflux condenser, heating device and agitator 0.02 mol of 3-morpholino-2-aza-thioarylic acid are obtained diphenylamide (Va), 0.01 mol 1,4-bibromobutan-2,3-dione and 60 ml Acetic anhydride suspended and refluxed for one hour. It is then cooled, suction filtered and dried. Yield be carries 65%. Mp: 262 ° C.

b) 1,2-di- (5-diphenylamino-4-phenyl-2-thienyl) ethanedione VIb

In a flask with a reflux condenser, heating device and agitator 0.02 mol of 3-morpholino-2-phenyl-thioarylic acid are obtained diphenylamide (Vb), 0.01 mol 1,4-bibromobutan-2,3-dione and 60 ml Acetic anhydride suspended and refluxed for one hour. It is then cooled, suction filtered and dried. Yield be carries 68%. Mp: 183-186 ° C.

Type VII compounds a) 2,3-Di- (5-diphenylamino-2-thiazolyl) quinoxaline VIIa

In a flask with a reflux condenser, heating device and agitator 0.02 mol of 1,2-di- (5-diphenylamino-1,3-thiazole-2- yl) -ethanedione VIa, 0.01 mol of 1,2-phenylenediamine and 60 ml of di suspended methylformamide and a 2 hour reflux hitzt. It is then cooled, suction filtered and dried. from loot is 68%. Mp: 221 ° C.

b) 2,3-di- (5-diphenylamino-4-phenyl-2-thienyl) quinoxaline VIIb

In a flask with a reflux condenser, heating device and agitator 0.02 mol of 1,2-di- (5-diphenylamino-4-phenyl-2- thienyl) -ethanedione VIb, 0.01 mol of 1,2-phenylenediamine and 60 ml Dimethylformamide suspended and reflux for one hour hitzt. It is then cooled, suction filtered and dried. from loot is 68%. Mp: 140 ° C.

Type VIII compounds a) 1,1-Di - [(2-N, N-diphenylamino) -1,3-thiazol-5-yl)] - 2,2- dicyanoethylene VIIIa

In a 100 ml flask with stirrer, heater and back flow cooler 1.13 g (= 0.0043 mol) 1,1-di- (bromomethyl) - 2,2-dicyano-ethylene together with 2.77 g (= 0.0086 mol) 3- Morpholino-2-aza-thioarylic acid diphenylamide (Va) in 50 ml THF dissolved and heated at reflux for 10 h. After the reak has ended tion is cooled, from the by-product (Morholi niumhydrobromid) aspirated and turned on the rotary evaporator concentrated. Finally, column chromatography is carried out over silica gel. The yield is 47%. Mp = 218 ° C

b) 1,1-di- [2- (N, N-diphenylamino-3-phenyl) thiophene-5-yl] -2,2- dicyanoethylene VIIIb

In a 100 ml flask with stirrer, heater and back flow coolers become 0.89 g (= 0.0034 mol) 1,1-di- (bromomethyl) - 2,2-dicyano-ethylene together with 2.7 g (= 0.0068 mol) 3- Morpholino-2-phenyl-thioacrylic acid diphenylamide (Vb) in 50 ml Dissolved THF and heated at reflux for 10 h. After finished The reaction is cooled, from the by-product formed (Morholinium hydrobromide) suctioned off and on a rotary evaporator concentrated. This is followed by column chromatographic purification of the product over silica gel. The yield is 55%. Mp. = 201 ° C

Claims (14)

1. 5-acceptor-functionalized 2-N, N-diarylamino-thiophene or -thiazole IV
where the following applies:
R ¹ , R ² and R ³ are - independently of one another - each a monofunctional (het) aryl system, i.e. a conjugated carbocyclic or heterocyclic ring system, which can also consist of linear or angularly fused or linked identical or different ring types, the peripheral hydrogen atoms can optionally be substituted by alkyl, alkoxy, phenoxy, dialkylamino or diphenylamino groups (alkyl = C ₁ to C ₆ );
R ¹ can also be a corresponding bifunctional (het) aryl lens system, ie a conjugated carbocyclic or heterocyclic ring system which can also consist of linearly or angularly fused or linked identical or different ring types, the peripheral hydrogen atoms being optionally substituted by alkyl, alkoxy , Phenoxy, di alkylamino or diphenylamino groups (alkyl = C ₁ to C ₆ ) may be substituted;
X, which has the meanings -N = and -CR ⁸ =, where R ^{8 has} the meaning of R ² or hydrogen.
R ⁴ and R ⁵ , which can be the same or different, but represent a complex or complex group with electron acceptor character, which together with the C atom connecting both substituents are all derived from malonic acid and its cyclic ureides and thiouroids can understand; Accordingly, R ⁴ and R ^{5 can be} nitrile groups, carboxylic acid ester groups, and carboxylic acid reamide groups, where the ester, amide or ureide residues can include branched or unbranched alkyl residues with up to 10 carbon atoms, triphenylmethyl residues (trityl residues) and R ² could be. 2. 2,3-Dihetarylquinoxaline VII of the general structure
wherein R ¹ , R ² and X have the meaning given in claim 1 and
Y can be carbon or nitrogen, where at
Y = C can be fused independently of one another on the bonds c, d and e further aromatic ring structures; at
Y = N further aromatic ring structures can be fused to the bond d. 3. 1,1-Bishetaryl-2,2-bis-acceptor substituted ethylene VIII of the general structure
wherein R ¹ , R ² , R ⁴ , R ⁵ and X have the meaning given in claim 1. 4. 2,3-dihetarylquinoxaline according to claim 2, wherein the 2,3- Dihetarylquinoxaline polymer is present. 5. Substituted ethylene according to claim 3, wherein the substi tuated ethylene polymer is present. 6. A process for the preparation of the 2-N, N-diarylamino-thiophene or thiazole IV, characterized by the following steps:

• a) implementation of a thiocarboxamide I with an ω-haloacylarene to a 2-N, N-diarylamino-thiophene or thi azole II
• b) reaction of the compound II via a Vilsmeier reaction with dimethylformamide and acid chloride to a 5-formyl-2-N, N-diarylamino-thiophene or -thiazole III and
• c) condensation of compound III with a malonic acid derivative to IV.

7. Process for the preparation of 2,3-dihetarylquinoxaline VII, characterized by the following steps:

• a) reaction of a thiocarboxamide I with orthoformic acid ester and a secondary amine to a 3-amino thioacrylic acid amide or the 2-aza-analog derivative V
• b) conversion of V in the presence of 1,4-dibromobutane-2,3-dione by S-alkylation to a hetarylbenzene derivative VI and
• c) Reaction of VI with an ortho-diaminoarylene derivative to the final product VII.

8. Process for the preparation of the 1,1-bishetaryl-2,2- bisacceptor-substituted ethylene VIII characterized by following step: Implementation of a 3-amino-thioacrylic acid amide or 2-aza analog derivative V with a 2,2-bishalomethyl vinylidene malonic acid derivative to VIII. 9. The method of claim 7, wherein the secondary amine is one Has a boiling point of at least 100 ° C. 10. The method according to any one of claims 6 to 9, wherein the radical R ^{1 has} a bifunctional structure. 11. Use of a connection according to one of claims 1 to 5 in organic light emitting diodes (OLED). 12. Use of a connection according to one of claims 1 to 5 as a semiconducting material in an electronic or microelectronic component. 13. Production of an organic light-emitting diode, the light-emitting layer by evaporating one of the connins is made of claims 1 to 5. 14. Production of an organic light-emitting diode, the light-emitting layer by spin coating one of the verbin manures according to one of claims 1 to 5 is produced.