Polycyclic compounds for organic electroluminescent devices

Abstract

The invention relates to compounds which are suitable for use in electronic devices, and to electronic devices, in particular organic electroluminescent devices, containing said compounds.

Claims

1. A compound comprising at least one structure of the formula (I): ##STR00403## where the symbols and indices used are as follows: Z is N, P, B, Al, P(O), P(S) or Ga; Y.sup.1, Y.sup.2, Y.sup.3 is a bond, N(Ar), N(R), P(Ar), P(R), P(O)Ar, P(O)R, P(S)Ar, P(S)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), CO, C(R).sub.2, Si(R).sub.2, CNR, CNAr, CC(R).sub.2, O, S, Se, SO, or SO.sub.2; p.sup.2, p.sup.3 are the same or different and are 0 or 1; X is N, CR, or C if a Y.sup.1, Y.sup.2 or Y.sup.3 group binds thereto, with the proviso that not more than two of the X groups in one cycle are N; R is the same or different at each instance and is H, D, OH, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.1).sub.2, C(O)N(Ar).sub.2, C(O)N(R.sup.1).sub.2, C(Ar).sub.3, C(R.sup.1).sub.3, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(Ar).sub.2, B(R.sup.1).sub.2, C(O)Ar, C(O)R.sup.1, P(O)(Ar).sub.2, P(O)(R.sup.1).sub.2, P(Ar).sub.2, P(R.sup.1).sub.2, S(O)Ar, S(O)R.sup.1, S(O).sub.2Ar, S(O).sub.2R.sup.1, OSO.sub.2Ar, OSO.sub.2R.sup.1, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may in each case be substituted by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1CCR.sup.1, CC, Si(R.sup.1).sub.2, CO, CS, CSe, CNR.sup.1, C(O)O, C(O)NR.sup.1, NR.sup.1, P(O)(R.sup.1), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, two R radicals may also together form a ring system; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; at the same time, it is possible for two Ar radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.1), C(R.sup.1).sub.2, Si(R.sup.1).sub.2, CO, CNR.sup.1, CC(R.sup.1).sub.2, O, S, SO, SO.sub.2, N(R.sup.1), P(R.sup.1) and P(O)R.sup.1; R.sup.1 is the same or different at each instance and is H, D, F, Cl, Br, I, CN, NO.sub.2, N(Ar).sub.2, N(R.sup.2).sub.2, C(O)Ar, C(O)R.sup.2, P(O)(Ar).sub.2, P(Ar).sub.2, B(Ar).sub.2, B(R.sup.2).sub.2, C(Ar).sub.3, C(R.sup.2).sub.3, Si(Ar).sub.3, Si(R.sup.2).sub.3, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 40 carbon atoms or an alkenyl group having 2 to 40 carbon atoms, each of which may be substituted by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CS, CSe, CNR.sup.2, C(O)O, C(O)NR.sup.2, NR.sup.2, P(O)(R.sup.2), O, S, SO or SO.sub.2 and where one or more hydrogen atoms may be replaced by D, F, Cl, Br, I, CN or NO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms, each of which may be substituted by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or an aralkyl or heteroaralkyl group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals, or a combination of these systems; at the same time, two or more R.sup.1 radicals together may form a ring system; at the same time, one or more R.sup.1 radicals may form a ring system with a further part of the compound; Ar is the same or different at each instance and is an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, it is possible for two Ar radicals bonded to the same carbon atom, silicon atom, nitrogen atom, phosphorus atom or boron atom also to be joined together via a bridge by a single bond or a bridge selected from B(R.sup.2), C(R.sup.2).sub.2, Si(R.sup.2).sub.2, CO, CNR.sup.2, CC(R.sup.2).sub.2, O, S, SO, SO.sub.2, N(R.sup.2), P(R.sup.2) and P(O)R.sup.2; R.sup.2 is the same or different at each instance and is selected from the group consisting of H, D, F, CN, an aliphatic hydrocarbyl radical having 1 to 20 carbon atoms or an aromatic or heteroaromatic ring system which has 5 to 30 aromatic ring atoms and in which one or more hydrogen atoms may be replaced by D, F, Cl, Br, I or CN and which may be substituted by one or more alkyl groups each having 1 to 4 carbon atoms; at the same time, two or more substituents R.sup.2 together may form a ring system; with the proviso that if Z is selected from N and P, at least one of the Y.sup.1, Y.sup.2, Y.sup.3 groups is P(O)Ar, P(O)R, B(Ar), B(R), Al(Ar), Al(R), Ga(Ar), Ga(R), CO, SO or SO.sub.2, or if Z is selected from B, Al, P(O), P(S) and Ga, at least one of the Y.sup.1, Y.sup.2, Y.sup.3 groups is N(Ar), N(R), P(Ar), P(R), O, S or Se; characterized in that at least two R radicals form a fused ring together with the further groups to which the two R radicals bind, where the two R radicals form at least one structure of the formulae (RA-1) to (RA-12): ##STR00404## ##STR00405## where R.sup.1 has the definition set out above, the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R radicals bind, and the further symbols have the following definition: Y.sup.4 is the same or different at each instance and is C(R.sup.1).sub.2, (R.sup.1).sub.2CC(R.sup.1).sub.2, (R.sup.1)CC(R.sup.1), NR.sup.1, NAr, O or S; R.sup.a is the same or different at each instance and is F, a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 40 carbon atoms or an alkenyl or alkynyl group having 2 to 40 carbon atoms or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms, where the alkyl, alkoxy, thioalkoxy, alkenyl or alkynyl group may be substituted in each case by one or more R.sup.2 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.2CCR.sup.2, CC, Si(R.sup.2).sub.2, CO, CS, CSe, CNR.sup.2, C(O)O, C(O)NR.sup.2, NR.sup.2, P(O)(R.sup.1), O, S, SO or SO.sub.2, or an aromatic or heteroaromatic ring system which has 5 to 60 aromatic ring atoms and may be substituted in each case by one or more R.sup.2 radicals, or an aryloxy or heteroaryloxy group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.2 radicals; at the same time, it is also possible for two Ra radicals together to form a ring system; s is 0, 1, 2, 3, 4, 5 or 6; t is 0, 1, 2, 3, 4, 5, 6, 7 or 8; v is 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9.

2. A compound as claimed in claim 1, comprising at least one structure of the formulae (IIa), (IIb), (IIc) and (IId): ##STR00406## where p.sup.2, p.sup.3, Y.sup.1, Y.sup.2, Y.sup.3, X, Z, and R have the definitions given in claim 1, the index m is 0, 1, 2, 3 or 4, and the index n is 0, 1, 2 or 3.

3. A compound as claimed in claim 1, comprising at least one structure of the formulae (IIIa), (IIIb) and (IIIc): ##STR00407## where Y.sup.1, Y.sup.2, Y.sup.3, X, Z, and R have the definitions given in claim 1, the index 1 is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, and the index n is 0, 1, 2 or 3.

4. A compound as claimed in claim 1, characterized in that the at least two R radicals that form structures of the formulae (RA-1) to (RA-12) and form a condensed ring are R radicals from adjacent X groups.

5. A compound as claimed in claim 1, characterized in that at least two R radicals form a fused ring together with the further groups to which the two R radicals bind, where the two R radicals form at least one of the structures of the formulae (RA-1a) to (RA-4f): ##STR00408## ##STR00409## where the symbols R.sup.a and R.sup.1 and the indices s and t have the definition given in claim 1, and the index m is 0, 1, 2, 3 or 4.

6. A compound as claimed in claim 1, comprising at least one structure of the formulae (IVa) to (IVu): ##STR00410## ##STR00411## ##STR00412## ##STR00413## where Y.sup.1, Y.sup.2, Y.sup.3, X, Z, and R have the definitions given in claim 1, the symbol o represents the sites of attachment of at least one of the structures (RA-1) to (RA-12), the index 1 is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, the index n is 0, 1, 2 or 3, the index j is 0, 1 or 2, and the index k is 0 or 1.

7. A compound as claimed in claim 1, comprising at least one structure of the formulae (IVa-1) to (IVb-4): ##STR00414## ##STR00415## where the indices s and v and the symbols Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, X, Z, R, Ra and R.sup.1 have the definitions given in claim 1, the index n is 0, 1, 2 or 3, and the index k is 0 or 1.

8. A compound as claimed in claim 1, that at least two R radicals form a fused ring together with the further groups to which the two R radicals bind, where the two R radicals form of the structures of the formula (RB): ##STR00416## where R.sup.1 has the definition set out in claim 1, the index m is 0, 1, 2, 3 or 4, and Y.sup.5 is C(R.sup.1).sub.2, NR.sup.1, NAr, O or S.

9. A compound as claimed in claim 1, wherein the compounds have at least two fused rings, wherein at least one fused ring is formed by structures of the formulae (RA-1) to (RA-12) and a further ring is formed by structures of the formulae (RA-1) to (RA-12) or (RB), comprising at least one structure of the formulae (Va) to (Vz): ##STR00417## ##STR00418## ##STR00419## ##STR00420## ##STR00421## where Y.sup.1, Y.sup.2, Y.sup.3, X, Z, and R have the definitions given in claim 1, the symbol o represents the sites of attachment of at least one structure of the formulae (RA-1) to (RA-12) or a structure of the formula (RB), the index 1 is 0, 1, 2, 3, 4 or 5, the index m is 0, 1, 2, 3 or 4, the index n is 0, 1, 2 or 3, the index j is 0, 1 or 2, and the index k is 0 or 1.

10. A compound as claimed in claim 1, comprising at least one structure of the formulae (IVe-1) to (Ivh-4): ##STR00422## ##STR00423## ##STR00424## ##STR00425## where the indices s and v, Y.sup.1, Y.sup.2, Y.sup.4, X, Z, R, R.sup.a and R.sup.1 have the definitions given in claim 1, the index m is 0, 1, 2, 3 or 4, the index n is 0, 1, 2 or 3, the index j is 0, 1 or 2, and the index k is 0 or 1.

11. A compound as claimed in claim 1, comprising at least one structure of the formulae (Va-1) to (Va-18): ##STR00426## ##STR00427## ##STR00428## ##STR00429## where the indices s and v, Y.sup.1, Y.sup.2, Y.sup.3, Y.sup.4, Y.sup.5, X, Z, R, R.sup.a and R.sup.1 have the definitions given in claim 1, the index m is 0, 1, 2, 3 or 4, the index n is 0, 1, 2 or 3, and the index k is 0 or 1.

12. A compound as claimed in claim 1, characterized in that, in the formulae (I), the sum total of the indices p.sup.2 and p.sup.3 is 2 and at least one of the Y.sup.1, Y.sup.2, Y.sup.3 groups is a bond, at least one of the Y.sup.1, Y.sup.2, Y.sup.3 group(s) is B(Ar) or B(R) and Z is N.

13. A compound as claimed in claim 1, characterized in that, in the formulae (I), the sum total of the indices p.sup.2 and p.sup.3 is 2 and at least two of the Y.sup.1, Y.sup.2, Y.sup.3 groups are B(Ar) or B(R) and Z is N.

14. A compound as claimed in claim 1, characterized in that, in the formulae (I), the sum total of the indices p.sup.2 and p.sup.3 is 2 and at least one of the Y.sup.1, Y.sup.2, Y.sup.3 groups is a bond, at least one of the Y.sup.1, Y.sup.2, Y.sup.3 groups is N(Ar) or N(R) and Z is B.

15. A compound as claimed in claim 1, characterized in that, in the formulae (I), the sum total of the indices p.sup.2 and p.sup.3 is 2 and at least two of the Y.sup.1, Y.sup.2, Y.sup.3 groups are N(Ar) or N(R) and Z is B.

16. A compound as claimed in claim 1, characterized in that, in the formulae (I), the sum total of the indices p.sup.2 and p.sup.3 is 1 or the index p.sup.2 is 1 and at least one of the Y.sup.1, Y.sup.2, Y.sup.3 groups is B(Ar) or B(R) and Z is N.

17. A compound as claimed in claim 1 characterized in that, in the formulae (I), the sum total of the indices p.sup.2 and p.sup.3 is 1 or the index p.sup.2 is 1 and at least one of the Y.sup.1, Y.sup.2, Y.sup.3 groups is N(Ar) or N(R) and Z is B.

18. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 1, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

19. A formulation comprising at least one compound as claimed in claim 1 and at least one further compound.

20. A composition comprising at least one compound as claimed in claim 1 and at least one further compound selected from the group consisting of fluorescent emitters, phosphorescent emitters, emitters that exhibit TADF, host materials, electron transport materials, electron injection materials, hole conductor materials, hole injection materials, electron blocker materials and hole blocker materials.

21. A process for preparing a compound as claimed in claim 1, characterized in that a base skeleton having a Z group or a precursor of the Z group is synthesized, and at least one of the Y.sup.1, Y.sup.2, Y.sup.3 groups is introduced by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

22. An electronic device comprising the compound as claimed in claim 1.

23. An electronic device comprising at least one compound as claimed in claim 1, wherein the electronic device is an electroluminescent device.

Description

EXAMPLES

(1) The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. The metal complexes are additionally handled with exclusion of light or under yellow light. The solvents and reagents can be purchased, for example, from Sigma-ALDRICH or ABCR. The Respective figures in square brackets or the numbers quoted for individual compounds relate to the CAS numbers of the compounds known from the literature. In the case of compounds that can have multiple enantiomeric, diastereomeric or tautomeric forms, one form is shown in a representative manner.

Synthesis of Synthons S

Example S1

(2) ##STR00103##

(3) A well-stirred mixture of 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 32.4 g (100 mmol) of 2-(6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononen-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane [1801624-63-4], 63.7 g (300 mmol) of tripotassium phosphate, 1.83 g (6 mmol) of tri-o-tolylphosphine, 225 mg (1 mmol) of palladium(II) acetate, 350 ml of toluene, 80 ml of dioxane and 300 ml of water is heated under reflux for 16 h. After cooling, the organic phase is separated from the aqueous phase and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution, and then dried over magnesium sulfate. The desiccant is filtered off using a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness. The glassy residue is recrystallized from isopropanol. Yield: 30.8 g (78 mmol) 78%. Purity by .sup.1H NMR about 97%.

(4) The following compounds can be prepared analogously:

(5) TABLE-US-00001 Ex. Reactants Product Yield S2 04 1801624-95-2 05 73% 06 1801624-60-1 S3 07 1801624-96-3 08 75% 09 1801624-61-2 S4 0 20712-00-9 1803458-55-0 68% S5 27452-17-1 80% 169126-63-0 S6 1801624-95-2 78% 169126-63-0 S7 97586-28-2 0 Use of 2 mmol of S-Phos rather than tri-o-tolylphosphine 54% Prep. from 97586-28-2 by Pd-catalyzed borylation with B.sub.2Pin.sub.2/KOAc/S- Phos/Pd(OAc).sub.2

Example S50

(6) ##STR00122##

(7) To a well-stirred solution of 39.5 g (100 mmol) of S1 in 500 ml of dichloromethane are added 100 mg of iron powder and then dropwise, in the dark over the course of 3 h, a mixture of 6.4 ml (240 mmol) of bromine and 100 ml of dichloromethane. After the addition has ended, the mixture is stirred under reflux for 4 h and at room temperature for 8 h. 200 ml of sat. sodium sulfite solution is added to destroy excess bromine, and the organic phase is separated off, washed with 500 ml of water and 300 ml of sat. sodium hydrogencarbonate solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness and the red viscous residue is recrystallized from about 500 ml of isopropanol. Yield: 33.7 g (61 mmol) 61%; purity: about 97% by .sup.1H NMR.

(8) The following compounds can be prepared analogously:

(9) TABLE-US-00002 Ex. Reactants Product Yield S51 S2 65% S52 S3 60% S53 S4 48% S54 S5 0 69% S55 S6 66% S56 S7 Boil at ambient humidity for 20 h 43%

Example S100

(10) ##STR00135##

(11) Preparation analogous to K. Nozaki et al., Angew. Chem., IE, 42(18), 2051-2053, 2003. To a well-stirred mixture of 55.2 g (100 mmol) of S50, 16.4 g (110 mmol) of 4-tert-butylaniline [769-92-6], 24.1 g (250 mmol) of sodium tert-butoxide in 1000 ml of toluene are added 405 mg (2 mmol) of tri-tert-butylphosphine [131274-22-1] and then 404 mg (1.8 mmol) of palladium(II) acetate, and the mixture is then stirred at 80 C. for 24 h. After cooling, the reaction mixture is washed three times with 500 ml each time of water. The organic phase is dried over magnesium sulfate, the magnesium sulfate is filtered therefrom by filtration through a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau. Yield: 36.3 g (67 mmol) 67%; purity: about 97% by .sup.1H NMR.

(12) The following compounds can be prepared analogously:

(13) TABLE-US-00003 Ex. Reactants Product Yield S101 S51 106-49-0 70% S102 S52 0 92-67-1 68% S103 S53 27856-10-6 57% S104 S54 1459-48-9 69% S105 S55 4106-66-5 0 72% S106 S56 92-67-1 55%

Example S150

(14) ##STR00154##

(15) To a well-stirred mixture of 36.8 g (100 mmol) of 1,2,3,5-tetrahydro-1,1,2,2,3,3-hexamethyl-8-phenylcyclopenta[b]carbazole [2082697-87-6], 16.4 g (110 mmol) of 4-tert-butylaniline [769-92-6], 12.1 g (125 mmol) of sodium tert-butoxide in 1000 ml of toluene are added 405 mg (2 mmol) of tri-tert-butylphosphine [131274-22-1] and then 404 mg (1.8 mmol) of palladium(II) acetate, and the mixture is then stirred at 100 C. for 16 h. After cooling, the reaction mixture is washed three times with 500 ml each time of water. The organic phase is dried over magnesium sulfate, the magnesium sulfate is filtered therefrom by filtration through a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau. Yield: 43.9 g (88 mmol) 88%; purity: about 97% by .sup.1H NMR.

(16) The following compounds can be prepared analogously:

(17) TABLE-US-00004 Ex. Reactants Product Yield S151 2222091-63-4 81974-62-1 83% S152 2082698-53-9 74768-89-1 0 85% S153 2082698-41-5 86-76-0 78% S154 2082698-52-8 32591-43-8 80%

Example S200

(18) ##STR00167##

(19) To a well-stirred mixture of 54.0 g (100 mmol) of S100, 1000 ml of glacial acetic acid and 1000 ml of dichloromethane (DCM) is added dropwise, at room temperature in the dark, a mixture of 10.8 ml (210 mmol) of bromine and 200 ml of DCM, and then the mixture is stirred for a further 24 h. 200 ml of saturated sodium sulfite solution and 500 ml of water are added, and the organic phase is separated off and washed three times with 500 ml each time of water and once with saturated sodium chloride solution. 500 ml of methanol is added and the DCM distilled off under reduced pressure, in the course of which the product crystallizes out. The crystals are filtered off with suction, washed three times with 100 ml each time of methanol and dried under reduced pressure. Recrystallization from toluene or from acetonitrile, with addition of DCM. Drying at T180 C., p10.sup.3 mbar. Yield: 62.8 g (90 mmol) 90%; purity: about 97% by .sup.1H NMR.

(20) The following compounds can be prepared analogously:

(21) TABLE-US-00005 Ex. Reactant Product Yield S201 S101 88% S202 0 S102 56% S203 S103 85% S204 S104 61% S205 S105 77% S206 S150 59% S207 0 S151 55% S208 S152 63% S209 S153 57% S210 S154 53% S211 S155 21%

Example S250

(22) ##STR00190##

(23) To a well-stirred mixture of 27.2 g (100 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 5.3 g (50 mmol) of 4-methylaniline [106-49-0], 24.2 g (250 mmol) of sodium tert-butoxide in 600 ml of toluene are added 405 mg (2 mmol) of tri-tert-butylphosphine [131274-22-1] and then 404 mg (1.8 mmol) of palladium(II) acetate, and the mixture is then stirred at 110 C. for 16 h. After cooling, the reaction mixture is washed three times with 500 ml each time of water. The organic phase is dried over magnesium sulfate, the magnesium sulfate is filtered therefrom by filtration through a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau. Yield: 20.0 g (41 mmol) 82%; purity: about 97% by .sup.1H NMR.

(24) The following compounds can be prepared analogously:

(25) TABLE-US-00006 Ex. Reactant Product Yield S251 1801624-95-2 769-92-6 84% S252 1801624-96-3 371-40-4 78% S253 1562418-80-7 92-67-1 79% S254 00 1801624-95-2 01 1562418-80-7 02 372-39-4 03 Two-stage one-pot process: Stage 1: 50 mmol bromide1 50 mmol aniline 1 mmol (DPPF)PdCl.sub.2 Stage 2: 50 mmol bromide2 2 mmol tri-tert-butylphosphine 1.8 mmol Pd(OAc).sub.2 63% S255 04 1801624-96-3 05 1190360-23-6 06 68693-08-3 07 Two-stage one-pot process: Stage 1: 50 mmol bromide1 50 mmol aniline 1 mmol (DPPF)PdCl.sub.2 Stage 2: 50 mmol bromide2 2 mmol tri-tert-butylphosphine 1.8 mmol Pd(OAc).sub.2 67% S256 08 97586-28-2 09 769-92-6 0 45%

Example S300

(26) ##STR00211##

(27) To a well-stirred mixture of 50.0 g (100 mmol) of S250 in 500 ml of THE is added, at +5 C. in the dark, 35.6 g (200 mmol) of N-bromosuccinimide in portions, and then the mixture is stirred for a further 4 h. The THF is largely removed under reduced pressure and 300 ml of methanol is added, the mixture is stirred for a further 30 min, and the crude product is filtered off with suction, washed three times with 50 ml each time of methanol and dried under reduced pressure. Purification is effected by recrystallization from acetonitrile with addition of DCM or by flash chromatography, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau. Drying at T160 C., p10-3 mbar. Yield: 48.0 g (73 mmol) 73%; purity: about 95% by .sup.1H NMR.

(28) The following compounds can be prepared analogously:

(29) TABLE-US-00007 Ex. Reactant Product Yield S301 S251 64% S302 S252 70% S303 S253 61% S304 S254 73% S305 0 S255 45% S350 S251 3.3 eq NBS 36% S351 S256 38%

Example S400

(30) ##STR00226##

(31) To a well-stirred mixture of 13.6 g (50 mmol) of 2-bromo-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 13.9 g (50 mmol) of 2-amino-6,7,8,9,10,11-hexahydro-5,9:7,11-dimethano-5H-benzocyclononene [1801624-97-4], 5.8 g (60 mmol) of sodium tert-butoxide in 300 ml of toluene is added 732 mg (1 mmol) of bis(diphenylphosphino)ferrocenepalladium(II) chloride [72287-62-4], and then the mixture is stirred at 110 C. for 16 h. After cooling, the reaction mixture is washed three times with 500 ml each time of water. The organic phase is dried over magnesium sulfate, the magnesium sulfate is filtered therefrom by filtration through a silica gel bed in the form of a toluene slurry, and the filtrate is concentrated to dryness under reduced pressure. The residue is subjected to flash chromatography, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau. Yield: 18.4 g (45 mmol) 90%; purity: about 97% by .sup.1H NMR.

(32) The following compounds can be prepared analogously:

(33) TABLE-US-00008 Ex. Reactant Product Yield S401 1801624-95-2 41024-99-1 93% S402 0 1801624-96-3 116233-23-9 89% S403 20712-00-9 31997-11-2 83% S404 27452-17-1 92050-16-3 86% S405 169695-24-3 0 50593-97-0 87% S406 1562418-80-7 2082698-39-1 89% S407 62-53-3 91% S408 1801624-95-2 92-67-1 0 93% S409 1801624-96-3 134-32-7 88% S410 169695-24-3 50548-43-1 79%

Example S450

(34) ##STR00257##

(35) A mixture of 45.1 g (110 mmol) of S400, 11.3 g (50 mmol) of 1-bromo-2,3-dichlorobenzene [56961-77-4], 12.5 g (130 mmol) of sodium tert-butoxide [865-48-5], 354 mg (0.5 mmol) of (amphos).sub.2PdCl.sub.2 [887919-35-9] and 200 ml of o-xylene is stirred at 80 C. for 3 h and then at 130 C. for 6 h. After cooling, the reaction mixture is admixed with 500 ml of ethyl acetate and 500 ml of water, and the organic phase is removed, washed once with 500 ml of water and twice with 300 ml each time of saturated sodium chloride solution, and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of an ethyl acetate slurry, the filtrate is concentrated to dryness, the residue is boiled with 300 ml of ethanol, the solids are filtered off, and these are washed twice with 50 ml of ethanol and dried under reduced pressure. Yield: 29.3 g (31.5 mmol) 63%; purity: about 95% by .sup.1H NMR.

(36) The following compounds can be prepared analogously:

(37) TABLE-US-00009 Ex. Reactant Product Yield S451 65% 0 S452 67% S453 60% S454 58% S455 0 65% S456 63% S457 63% S458 0 70% S459 57% S460 68% S461 51% 0

Example, Dopant D1

(38) The sequence that follows is conducted as a three-stage one-pot reaction.

Step 1: Lithiation of S200

(39) ##STR00292##

(40) A baked-out, argon-inertized four-neck flask with magnetic stirrer bar, dropping funnel, water separator, reflux condenser and argon blanketing is charged with 34.9 g (50 mmol) of S200 in 1700 ml of tert-butylbenzene. The reaction mixture is cooled down to 40 C., and then 110.5 ml (210 mmol) of tert-butyllithium, 1.9 M in n-pentane, is added dropwise. The mixture is stirred at 40 C. for a further 30 min, allowed to warm up to room temperature, then heated to 70 C., in the course of which the n-pentane is distilled off via the water separator over about 1 h.

Step 2: Transmetalation and Cyclization

(41) ##STR00293##

(42) The reaction mixture is cooled back down to 40 C. 10.4 ml (110 mmol) of boron tribromide is added dropwise over a period of about 10 min. On completion of addition, the reaction mixture is stirred at RT for 1 h. Then the reaction mixture is cooled down to 0 C., and 19.2 ml (110 mmol) of diisopropylethylamine is added dropwise over a period of about 30 min. Then the reaction mixture is stirred at 160 C. for 16 h. After cooling, diisopropylethylammonium hydrobromide is filtered off with suction using a double-ended frit, and the filtrate is cooled down to 78 C.

Step 3: Arylation to D1

(43) ##STR00294##

(44) A second baked-out, argon-inertized Schlenk flask with magnetic stirrer bar is charged with 27.8 g (150 mmol) of 2-bromo-1,3-dimethylbenzene [576-22-7] in 1000 ml of diethyl ether and cooled down to 78 C. 60.0 ml (150 mmol) of n-butyllithium, 2.5 M in n-hexane, is added dropwise thereto over about 20 min and the mixture is stirred for a further 30 min. The reaction mixture is allowed to warm up to RT and stirred for a further 1 h, and the solvent is removed completely under reduced pressure. The lithium organyl is suspended in 300 ml of toluene and transferred into the cryogenic reaction mixture from step 2. The mixture is stirred for a further 1 h, and the reaction mixture is left to warm up to RT overnight. 15 ml of acetone is added cautiously to the reaction mixture, which is concentrated to dryness. The oily residue is absorbed with DCM onto ISOLUTE and hot-filtered through a silica gel bed with an n-pentane-DCM mixture (10:1). The filtrate is concentrated to dryness. The residue is subjected to flash chromatography twice, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau. Further purification is effected by repeated hot extraction crystallization with acetonitrile and final fractional sublimation or heat treatment under reduced pressure. Yield: 16.1 g (21 mmol) 42%; purity: about 99.9% by .sup.1H NMR.

(45) The following compounds can be prepared analogously:

(46) TABLE-US-00010 Ex. Reactants Product Yield D2 38% D3 24% 00 D4 01 02 35% 03 D5 04 05 21% 06 D6A 07 08 12% D6B 09 0 15% D7 24% D8 15% D9 23% D10 0 8% D11 13% D12 31% D13 0 20% D14 34% D15 27% D16 25% 0 D17 31% D18 7% D50A 45% D50B 14% D51A 0 43% D51B 11% D52 23% D53 28% D54 0 30% D55 13% D56 16% D57 0 12%

Example, Dopant D100

Step 1: Lithiation of S450

(47) ##STR00371##

(48) A baked-out, argon-inertized four-neck flask with magnetic stirrer bar, dropping funnel, water separator, reflux condenser and argon blanketing is charged with 46.4 g (50 mmol) of S450 and 200 ml of tert-butylbenzene, and cooled to 40 C. 64.7 ml (110 mmol) of tert-butyllithium, 1.7 M in n-pentane, is added dropwise to the mixture over 10 min. The reaction mixture is allowed to warm up to room temperature and stirred at 60 C. for a further 3 h, in the course of which the n-pentane is distilled off via the water separator.

Step 2: Transmetalation and Cyclization

(49) ##STR00372##

(50) The reaction mixture is cooled back down to 40 C. 5.7 ml (60 mmol) of boron tribromide is added dropwise over a period of about 10 min. On completion of addition, the reaction mixture is stirred at RT for 1 h. Then the reaction mixture is cooled down to 0 C., and 21.0 ml (120 mmol) of diisopropylethylamine is added dropwise over a period of about 30 min. Then the reaction mixture is stirred at 130 C. for 5 h. After cooling, the mixture is diluted with 500 ml of toluene and hydrolyzed by addition of 300 ml of aqueous 10% by weight potassium acetate solution, and the organic phase is removed and concentrated to dryness under reduced pressure. The oily residue is absorbed with DCM onto ISOLUTE and hot-filtered through a silica gel bed with an n-pentane-DCM mixture (10:1). The filtrate is concentrated to dryness. The residue is subjected to flash chromatography twice, silica gel, n-heptane/ethyl acetate, Torrent automated column system from A. Semrau. Further purification is effected by repeated hot extraction crystallization with acetonitrile and final fractional sublimation or heat treatment under reduced pressure. Yield: 18.5 g (20.5 mmol) 41%; purity: about 99.9% by .sup.1H NMR.

(51) The following compounds, can be prepared analogously:

(52) TABLE-US-00011 Ex. Reactant Product Yield D101 43% D102 42% D103 44% D104 0 35% D105 42% D106 40% D107 36% D108 _ 47% D109 0 30% D110 35% D111 30%
1) Vacuum-Processed Devices:

(53) OLEDs of the invention and OLEDs according to the prior art are produced by a general method according to WO 2004/058911, which is adapted to the circumstances described here (variation in layer thickness, materials used).

(54) In the examples which follow, the results for various OLEDs are presented. Cleaned glass plates (cleaning in Miele laboratory glass washer, Merck Extran detergent) coated with structured ITO (indium tin oxide) of thickness 50 nm are pretreated with UV ozone for 25 minutes (PR-100 UV ozone generator from UVP) and, within 30 min, for improved processing, coated with 20 nm of PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate), purchased as CLEVIOS P VP Al 4083 from Heraeus Precious Metals GmbH Deutschland, spun on from aqueous solution) and then baked at 180 C. for 10 min. These coated glass plates form the substrates to which the OLEDs are applied.

(55) The OLEDs basically have the following layer structure: substrate/hole injection layer 1 (HIL1) consisting of Ref-HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm/hole transport layer 1 (HTL1) composed of 160 nm of HTM1/emission layer (EML) 20 nm/hole blocker layer (HBL) 10 nm/electron transport layer (ETL) 20 nm/electron injection layer (EIL) composed of 1 nm of ETM2/and finally a cathode. The cathode is formed by an aluminum layer of thickness 100 nm.

(56) First of all, vacuum-processed OLEDs are described. For this purpose, all the materials are applied by thermal vapor deposition in a vacuum chamber. In this case, the emission layer always consists of at least one matrix material (host material) and an emitting dopant (emitter) which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as SMB1:D1 (95:5%) mean here that the material SMB1 is present in the layer in a proportion by volume of 95% and D1 in a proportion of 5%. Analogously, the electron transport layer may also consist of a mixture of two materials. The exact structure of the OLEDs can be found in table 1. The materials used for production of the OLEDs are shown in table 3.

(57) The OLEDs are characterized in a standard manner. For this purpose, the electroluminescence spectra, the current efficiency (measured in cd/A), the power efficiency (measured in lm/W) and the external quantum efficiency (EQE, measured in percent) are, as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian radiation characteristics. Electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and these are used to calculate the CIE 1931 y color coordinates.

(58) Use of compounds of the invention as materials in OLEDs:

(59) One use of the compounds of the invention is as dopant in the emission layer in OLEDs. Compounds according to table 3 are used as a comparison according to the prior art. The results for the OLEDs are collated in table 2.

(60) TABLE-US-00012 TABLE 1 Structure of the OLEDs Ex. EML HBL ETL Ref. 1 SMB1:D-Ref. 1 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) Ref. 2 SMB1:D-Ref. 2 ETM1 ETM:ETM2 (95%:5%) (50%:50%) SD1 SMB1:D1 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD2 SMB1:D2 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD5 SMB1:D5 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD6A SMB2:D6A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD6B SMB1:D6B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD10 SMB1:D10 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD11 SMB1:D11 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD12 SMB1:D12 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD13 SMB1:D13 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD14 SMB1:D14 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD15 SMB1:D15 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD16 SMB1:D16 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD17 SMB2:D17 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD18 SMB1:D18 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD50A SMB1:D50A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD51A SMB1:D51A ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD51B SMB1:D51B ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD54 SMB3:D54 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD56 SMB1:D56 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD57 SMB1:D57 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD100 SMB1:D100 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD101 SMB1:D101 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD104 SMB1:D104 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD106 SMB1:D106 ETM1 ETM1:ETM2 (95%:5%) (50%:50%) SD108 SMB1:D108 ETM1 ETM1:ETM2 (95%:5%) (50%:50%)

(61) TABLE-US-00013 TABLE 2 Results for the vacuum-processed OLEDs EQE (%) Voltage (V) CIE y EL-FWHM Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 1000 cd/m.sup.2 [nm] Ref. 1 7.0 4.6 0.19 36 Ref. 2 6.5 4.5 0.11 28 SD1 7.6 4.3 0.03 13 SD2 8.0 4.2 0.03 15 SD5 8.2 4.3 0.03 14 SD6A 7.4 4.2 0.07 15 SD6B 7.0 4.1 0.08 16 SD10 5.7 4.5 0.06 16 SD11 5.3 4.6 0.04 13 SD12 7.8 4.3 0.03 15 SD13 7.4 4.4 0.03 14 SD14 8.2 4.4 0.03 14 SD15 6.7 4.1 0.05 17 SD16 6.8 4.3 0.05 18 SD17 6.6 4.0 0.07 19 SD18 7.6 4.5 0.18 24 SD50A 8.4 4.2 0.15 29 SD51A 8.2 4.2 0.15 28 SD51B 8.0 4.3 0.16 30 SD54 5.3 4.6 0.15 29 SD56 8.5 4.2 0.08 19 SD57 7.6 4.5 0.17 23 SD100 7.2 4.2 0.10 24 SD101 7.0 4.3 0.08 22 SD104 7.4 4.3 0.10 24 SD106 5.2 4.6 0.09 23 SD108 7.5 4.2 0.11 24

(62) TABLE-US-00014 TABLE 3 List of materials used 00 01 02

(63) By comparison with the references, the inventive compounds show narrower electroluminescence spectra, recognizable by the smaller FWHM values (Full Width Half Maximumwidth of the emission spectra in nm at half the peak height). This leads to smaller CIE y color coordinates, corresponding to improved color purity. In addition, in some cases, they have higher efficiencies and lower operating voltages, which additionally leads to an improvement in power efficiency.