NITROGENOUS HETEROAROMATIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

The present invention relates to nitrogen-containing heteroaromatics suitable for use in electronic devices, and to electronic devices, especially organic electroluminescent devices, comprising these compounds.

Claims

1.-21. (canceled)

22. A compound comprising at least one structure of the formula (I), ##STR01027## where the symbols and indices used are as follows: X is the same or different at each instance and is N or CR.sup.b; 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.e).sub.2, C(?O)N(Ar).sub.2, C(?O)N(R.sup.e).sub.2, C(Ar).sub.3, C(R.sup.e).sub.3, Si(Ar).sub.3, Si(R.sup.e).sub.3, B(Ar).sub.2, B(R.sup.e).sub.2, C(?O)Ar, C(?O)R.sup.e, P(?O)(Ar).sub.2, P(?O)(R.sup.e).sub.2, P(Ar).sub.2, P(R.sup.e).sub.2, S(?O)Ar, S(?O)R.sup.e, S(?O).sub.2Ar, S(?O).sub.2R.sup.e, OSO.sub.2Ar, OSO.sub.2R.sup.e, 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 each be substituted by one or more R.sup.e radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.eC?CR.sup.e, C?C, Si(R.sup.e).sub.2, C?O, C?S, C?Se, C?NR.sup.e, C(?O)O, C(?O)NR.sup.e, NR.sup.e, P(?O)(R.sup.e), 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.e 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.e radicals, or an arylthio or heteroarylthio group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.e radicals, or a diarylamino, arylheteroarylamino, diheteroarylamino group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.e radicals, or an arylalkyl or heteroarylalkyl group which has 5 to 60 aromatic ring atoms and 1 to 10 carbon atoms in the alkyl radical and may be substituted by one or more R.sup.e radicals; at the same time, any R radical may form a ring system with a further group; 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.e 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.e), C(R.sup.e).sub.2, Si(R.sup.e).sub.2, C?O, C?NR.sup.e, C?C(R.sup.e).sub.2, O, S, S?O, SO.sub.2, N(R.sup.e), P(R.sup.e) and P(?O)R.sup.e; R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e 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 be substituted in each case by one or more R.sup.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C?CR.sup.1, C?C, Si(R.sup.1).sub.2, C?O, C?S, C?Se, C?NR.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.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals may also form a ring system together or with a further group; 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 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, C?O, C?NR.sup.1, C?C(R.sup.1).sub.2, O, S, S?O, 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.2C?CR.sup.2, C?C, Si(R.sup.2).sub.2, C?O, C?S, C?Se, C?NR.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, C?O, C?NR.sup.2, C?C(R.sup.2).sub.2, O, S, S?O, 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.

23. The compound according to claim 22, wherein at least one of the R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals are not H.

24. The compound according to claim 22, wherein at least one of the R.sup.a, R.sup.c radicals are 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.1 radicals, where one or more nonadjacent CH.sub.2 groups may be replaced by R.sup.1C?CR.sup.1, C?C, Si(R.sup.1).sub.2, C?O, C?S, C?Se, C?NR.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.

25. The compound according to claim 22, wherein the R radical is an aromatic or heteroaromatic ring system which has 5 to 13 aromatic ring atoms and may be substituted by one or more R.sup.e radicals.

26. The compound according to claim 22, wherein two R.sup.a radicals together with the further groups to which the two R.sup.a radicals bind form a fused ring, an aliphatic or heteroaliphatic ring having 3 to 20 ring atoms or an aromatic or heteroaromatic ring having 5 to 13 ring atoms.

27. The compound according to claim 22, wherein two R.sup.c radicals together with the further groups to which the two R.sup.c radicals bind form a fused ring, an aliphatic or heteroaliphatic ring having 3 to 20, or an aromatic or heteroaromatic ring having 5 to 13 ring atoms.

28. The compound according to claim 22, comprising at least one structure of the formulae (I-1) to (I-30), ##STR01028## ##STR01029## ##STR01030## ##STR01031## ##STR01032## ##STR01033## ##STR01034## where the symbols R.sup.a, R.sup.b, R.sup.c, R.sup.d and R.sup.e have the definitions given in claim 22 and the further symbols and indices used are as follows: X.sup.1 is the same or different at each instance and is N or CR.sup.e, with the proviso that not more than two of the X.sup.1 groups in one cycle are N; Y.sup.1 is the same or different at each instance and is C(R.sup.e).sub.2, (R.sup.e).sub.2CC(R.sup.e).sub.2, (R.sup.e)C?C(R.sup.e), NR.sup.e, NAr, O, S, SO, SO.sub.2, Se, P(O)R.sup.e, BR.sup.e or Si(R.sup.e).sub.2; n is 0, 1, 2 or 3; and m is 0, 1, 2, 3 or 4.

29. The compound according to claim 22, wherein at least two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals form at least one structure of the following formulae (Cy-1) to (Cy-10), ##STR01035## where R.sup.1 and R.sup.2 have the definitions given in claim 22, the dotted bonds represent the sites of attachment to the atoms of the groups to which the two R, R.sup.a, R.sup.c, R.sup.d, R.sup.e radicals bind, and in addition: Z.sup.1, Z.sup.3 is the same or different at each instance and is C(R.sup.3).sub.2, O, S, NR.sup.3 or C(?O); Z.sup.2 is C(R.sup.1).sub.2, O, S, NR.sup.1 or C(?O), where two adjacent groups Z.sup.2 represent CR.sup.1?CR.sup.1 or an ortho-bonded arylene or heteroarylene group having 5 to 14 aromatic ring atoms which may be substituted by one or more R.sup.1 radicals; G is an alkylene group which has 1, 2 or 3 carbon atoms and may be substituted by one or more R.sup.1 radicals, CR.sup.1?CR.sup.1 or an ortho-bonded arylene or heteroarylene group which has 5 to 14 aromatic ring atoms and may be substituted by one or more R.sup.1 radicals; R.sup.3 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.2C?CR.sup.2, C?C, Si(R.sup.2).sub.2, C?O, C?S, C?Se, C?NR.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 R.sup.3 radicals which are bonded to the same carbon atom together may form an aliphatic or aromatic ring system and thus span a spiro system; in addition, R.sup.3 may form a ring system with an R, R.sup.a, R.sup.c, R.sup.d, R.sup.e or R.sup.1 radical; with the proviso that no two heteroatoms in these groups are bonded directly to one another and no two C?O groups are bonded directly to one another.

30. The compound according to claim 22, wherein at least two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals form at least one structure of the formulae (RA-1) to (RA-13) ##STR01036## ##STR01037## 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, R.sup.a, R.sup.c, R.sup.d, R.sup.e radicals bind, and the further symbols have the following definition: Y.sup.2 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)C?C(R.sup.1), NR.sup.1, NAr, O or S; R.sup.f 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 in each case 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.2C?CR.sup.2, C?C, Si(R.sup.2).sub.2, C?O, C?S, C?Se, C?NR.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, two R.sup.f radicals together or one R.sup.f radical together with an R.sup.1 radical or with a further group may form a ring system; r is 0, 1, 2, 3 or 4; 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.

31. The compound according to claim 22, wherein at least two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals together with the further groups to which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d, R.sup.e radicals form the structures of the formula (RB) ##STR01038## where R.sup.1 has the definition set out in claim 22, the index m is 0, 1, 2, 3 or 4, and Y.sup.3 is C(R.sup.1).sub.2, NR.sup.1, NAr, BR.sup.1, BAr, O or S.

32. The compound according to claim 22, wherein R or Ar is the same or different at each instance and is selected from phenyl, biphenyl, terphenyl, quaterphenyl, fluorene, spirobifluorene, naphthalene, indole, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, indenocarbazole, indolocarbazole, pyridine, pyrimidine, pyrazine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, quinoxaline, phenanthrene or triphenylene, each of which may be substituted by one or more R.sup.e radicals.

33. The compound according to claim 22, wherein the compound is symmetric in relation to the R.sup.a and R.sup.c radicals.

34. The compound according to claim 22, wherein the R.sup.e and/or R.sup.d radical represents, comprises, or forms together with an R.sup.d or R.sup.e radical, at least one group selected from C(Ar).sub.3, C(R.sup.1).sub.3, Si(Ar).sub.3, Si(R.sup.1).sub.3, B(R.sup.1).sub.2.

35. The compound according to claim 28, wherein the compound comprises exactly two or exactly three structures of formula (I) and/or (I-1) to (I-30).

36. An oligomer, polymer or dendrimer containing one or more compounds as claimed in claim 22, wherein, rather than a hydrogen atom or a substituent, there are one or more bonds of the compounds to the polymer, oligomer or dendrimer.

37. A formulation comprising at least one compound according to claim 22 and at least one further compound.

38. A formulation comprising the oligomer, polymer or dendrimer according to claim 36 and at least one further compound.

39. A composition comprising at least one compound according to claim 22 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.

40. A composition comprising the oligomer, polymer or dendrimer according to claim 36 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.

41. The composition according to claim 39, wherein the at least one further compound is a TADF host material and/or at least one further compound is a phosphorescent emitter (triplet emitter), where the further compounds forms a hyperfluorescence system and/or hyperphosphorescence system with the compound.

42. The composition according to claim 40, wherein the at least one further compound is a TADF host material and/or at least one further compound is a phosphorescent emitter (triplet emitter), where the further compounds forms a hyperfluorescence system and/or hyperphosphorescence system with the oligomer, polymer or dendrimer.

43. A process for preparing the compound according to claim 22, which comprises synthesizing a base skeleton having an aminopyridine group and at least one aromatic or heteroaromatic radical is introduced.

44. An electronic device comprising at least one compound according to claim 22.

45. An electronic device comprising the oligomer, polymer or dendrimer according to claim 36.

Description

FIGURE

[0226] FIG. 1 shows the photoluminescence spectra (PL spectra) of compounds ES1, ES5, ES10 and 611, measured with a Hitachi F-4500 PL spectrometer in about 10.sup.?5 molar degassed toluene solution at room temperature (about 25? C.).

[0227] These abovementioned advantages are not accompanied by an inordinately high deterioration in the further electronic properties.

[0228] It should be pointed out that variations of the embodiments described in the present invention are covered by the scope of this invention. Any feature disclosed in the present invention may, unless this is explicitly ruled out, be exchanged for alternative features which serve the same purpose or an equivalent or similar purpose. Thus, any feature disclosed in the present invention, unless stated otherwise, should be considered as an example of a generic series or as an equivalent or similar feature.

[0229] All features of the present invention may be combined with one another in any manner, unless particular features and/or steps are mutually exclusive. This is especially true of preferred features of the present invention. Equally, features of non-essential combinations may be used separately (and not in combination).

[0230] It should also be pointed out that many of the features, and especially those of the preferred embodiments of the present invention, should themselves be regarded as inventive and not merely as some of the embodiments of the present invention. For these features, independent protection may be sought in addition to or as an alternative to any currently claimed invention.

[0231] The technical teaching disclosed with the present invention may be abstracted and combined with other examples.

[0232] The invention is illustrated in more detail by the examples which follow, without any intention of restricting it thereby. The person skilled in the art will be able to use the information given to execute the invention over the entire scope disclosed and to prepare further compounds of the invention without exercising inventive skill and to use them in electronic devices or to employ the process of the invention.

EXAMPLES

[0233] The syntheses which follow, unless stated otherwise, are conducted under a protective gas atmosphere in dried solvents. 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 show multiple configurational isomers, enantiomers, diastereomers or tautomeric forms, one form is shown in a representative manner.

[0234] Synthesis Scheme Using the Example of a Homoadamantane Enamine:

##STR00637##

[0235] Steps 1 to 7 are conducted analogously to syntheses known from the literature: [0236] Step 1 to 4: M. Adachi et al., Tetrahedron Letters, 1996; 37 (49), 8871, EP 0 556 008 B1. [0237] Step 5: J. D. Eckelbarger et al., U.S. Pat. No. 8,835,409. E. A. Krasnokutskaya et al., Synthesis, 2007, 1, 81. [0238] Step 6: Variant 1: P. B. Tiruveedhula et al., Org. & Biomol. Chem., 2015, 13(43), 10705. K. Revunova et al., Polyhedron, 2013, 52, 1118. Variant 2: Y.-L- Tasi et al., J. Luminesc., 2007, 127, 41. [0239] Step 7: Variant 1: T. Kader et al., Chem. Eur. J., 2019, 25, 4412. Variant 2: A. W. Jones et al., Adv. Synth. Catal. 2015, 357, 945.

[0240] A: Preparation of the Synthons:

[0241] Synthesis of Enamines:

[0242] The enamines can be prepared by the process detailed in WO 2020/06466, page 108, from the ketones shown and morpholine in yields of about 60-80%, or are known from the literature.

TABLE-US-00011 Reactant Product Ex. Ketone/morpholine Enamine S1 [00638] [00639] 24669-56-5 S2 [00640] [00641] 2716-23-6 S3 [00642] [00643] 59117-09-8 S4 [00644] [00645] 6372-63-0 S5 [00646] [00647] 73164-06-4 S6 [00648] [00649] 497-38-1 S7 [00650] [00651] 464-48-2 (1S)-(?) S8 [00652] [00653] 15189-14-7 S9 [00654] [00655] 6308-02-7 S10 [00656] [00657] 1781-82-4 S11 [00658] [00659] 108-94-1 S12 [00660] [00661] 51209-49-5 S13 [00662] [00663] 5455-94-7 S14 [00664] [00665] 4694-115 S15 [00666] [00667] 96676-35-6 S16 [00668] [00669] 120-92-3 S17 [00670] [00671] 180690-80-6 S18 [00672] 124032-58-2 S19 [00673] [00674] 54193-73-6 S20 [00675] [00676] 126495-32-7 S21 [00677] 1195901-19-9 S22 [00678] 73129-56-3 S23 [00679] [00680] 26465-81-6 S24 [00681] [00682] 26465-81-6 S25 [00683] [00684] 36449-72-6 S26 [00685] [00686] 55010-17-8 S27 [00687] [00688] 866762-72-3 S28 [00689] 56639-83-9 S29 [00690] 4176-69-6 S30 [00691] 39665-41-9 S31 [00692] 196702-51-9 S32 [00693] 66216-87-6 S33 [00694] 122982-74-5 S34 [00695] 78347-86-1 S35 [00696] 344904-43-4 S36 [00697] 84736-44-7 S37 [00698] 345623-69-0 S38 [00699] 80384-86-7 S39 [00700] 164071-14-1

[0243] B) Synthesis of the Substituted Pyridines:

Step 1: Example S100

[0244] ##STR00701##

[0245] A mixture of 23.3 g (100 mmol) of S1, 22.6 g (120 mmol) of 4-(aminomethylene)-2-phenyl-5(4H)-oxazolone [3674-51-9], 47.3 ml (500 mmol) of acetic anhydride [108-24-7] and 150 ml of toluene is stirred at 100? C. for 4 h, analogously for the other 6- and 7-membered enamines, the 5-membered enamines are converted in o-xylene at 130? C./4 h in an autoclave. The mixture is concentrated completely under reduced pressure, 70 ml of methanol is added to the oil, the mixture is stirred for a further 3 h, and the crystallized product is filtered off with suction, washed once with 25 ml of ice-cold methanol and dried under reduced pressure. The crude product thus obtained is converted further without purification. Yield: 26.2 g (78 mmol), 78% E,Z isomer mixture with varying proportions, purity: about 95% by .sup.1H NMR.

Step 2: Example S200

[0246] ##STR00702##

[0247] A mixture of 33.4 g (100 mmol) S100 and 200 ml of 1-methyl-2-pyrrolidinone (NMP) is stirred at 200-205? C. for 1.5 h. The mixture is allowed to cool to about 100? C., the NMP is largely removed under reduced pressure, the glassy, viscous residue is taken up in 100 ml of warm acetonitrile, stirred at room temperature for a further 12 h, and the crystallite product is filtered off and dried under reduced pressure. Yield: 25.1 g (75 mmol), 75%; purity: about 95% by .sup.1H NMR.

Step 3: Example S300

[0248] ##STR00703##

[0249] To a suspension of 33.4 g (100 mmol) of S200 in a mixture of 150 ml of N,N-dimethylformamide (DMF) is added dropwise 14.0 ml (150 mmol) of phosphoryl chloride in 50 ml of DMF (caution: exothermic!), and then the mixture is stirred at room temperature for a further 16 h. The reaction mixture is poured cautiously onto 1000 ml of ice-water and stirred for a further 10 min, 200 ml of dichloromethane (DCM) is added, the mixture is stirred for a further 10 min, and the organic phase is removed. The aqueous phase is basified (pH 8-9) with cautious addition of conc. aqueous ammonia solution, the aqueous phase is extracted three times with 200 ml each time of ethyl acetate, and the combined ethyl acetate extracts are washed twice with 200 ml each time of ice-water, once with 200 ml of saturated sodium hydrogencarbonate solution and twice with 100 ml each time of saturated sodium chloride solution. The mixture is dried over a mixture of magnesium sulfate and sodium carbonate, the desiccant is filtered off, the organic phase is concentrated under reduced pressure and the residue is recrystallized once from acetonitrile with addition of ethyl acetate (EA). Yield: 24.7 g (81 mmol), 81%; purity: about 95% by .sup.1H NMR.

Step 4: Example S400

[0250] ##STR00704##

[0251] A mixture of 30.4 g (100 mmol) of S300, 100 ml of 3 N sulfuric acid and 200 ml of dioxane is stirred at 100? C. for 1.5 h. After cooling, the reaction mixture is diluted with 1000 ml of ice-water and then adjusted to pH ? 7.5 with 3 N NaOH while cooling with ice. The aqueous phase is extracted three times with 200 ml each time of DCM, and the combined organic phases are washed twice with 200 ml of water and once with 200 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off, the filtrate is concentrated to dryness and the solids are recrystallized from methanol. Yield: 23.1 g (93 mmol), 93%; purity: about 95% by .sup.1H NMR.

Step 5: Example S500

[0252] ##STR00705##

[0253] Variant 1:

[0254] 24.9 g (100 mmol) of S400 is introduced with good stirring into 500 ml of concentrated hydrochloric acid cooled to 3-5? C. To the suspension is added dropwise, with good stirring over the course of 15 min, a cooled solution of 10.4 g (150 mmol) of sodium nitrite in 50 ml of water, and then the mixture is stirred at 5? C. for about a further 20 min. The diazonium solution thus obtained is poured into a well-stirred solution, cooled to 5? C., of 90.0 g (600 mmol) of potassium iodide in 5000 ml of water to which 1000 ml of DCM has been added (caution: foaming!). After evolution of nitrogen has ended (about 25 min), sodium bisulfite solution is added until decolorization, and the pH is adjusted cautiously to ?7.5 with 5 N NaOH under very good cooling. The mixture is diluted with a further 1500 ml of DCM, the organic phase is removed, the aqueous phase is re-extracted twice with 500 ml each time of DCM, and the combined organic phases are washed twice with 500 ml each time of water and twice with 500 ml each time of saturated sodium chloride solution and then dried over magnesium sulfate. After the DCM has been removed under reduced pressure, the residue is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 22.9 g (63 mmol), 63%; purity: about 97% by .sup.1H NMR.

[0255] Variant 2:

[0256] To a solution of 24.9 g (100 mmol) of S400 in 500 ml of acetonitrile is added 57.1 g (300 mmol) of p-toluenesulfonic acid monohydrate [6192-52-5] in portions, and then the mixture is cooled to 10? C. in an ice bath. To the suspension is added in portions, with good stirring and ice cooling, a solution of 13.9 g (200 mmol) of sodium nitrite and 37.5 g (250 mmol) of potassium iodide in 60 ml of water, and the mixture is stirred at 10? C. for 15 min. The mixture is then allowed to warm up to room temperature and stirred for a further 70 min. Then the mixture is diluted with 1500 ml of water, adjusted to pH 9.5 by adding saturated sodium hydrogen carbonate solution and admixed with 200 ml of 2M sodium bisulfite solution. The precipitated crude product is filtered off with suction, washed twice with 50 ml each time of water and briefly dried by suction. The crude product is dissolved in 500 ml of DCM, the solution is dried over sodium sulfate, the desiccant is filtered off with suction and the crude product is applied to Isolute. Purification is effected by flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 25.0 g (72 mmol), 72%; purity: about 97% by 1H NMR.

[0257] The following pyridines can be obtained analogously to steps 1 to 5. Yield over five steps (step 1-5):

TABLE-US-00012 Ex. Enamine Product Yield S501 S2 [00706] 28% S502 S3 [00707] 25% S503 S4 [00708] 30% S504 S5 [00709] 23% S505 S6 [00710] 30% S506 S7 [00711] 26% S507 S8 [00712] 24% S508 S9 [00713] 26% S509 S10 [00714] 19% S510 S11 [00715] 34% S511 S12 [00716] 32% S512 S13 [00717] 18% S513 S14 [00718] 19% S514 S15 [00719] 15% S515 S16 [00720] 19% S516 S17 [00721] 23% S517 S18 [00722] 21% S518 S19 [00723] 20% S519 S20 [00724] 20% S520 S21 [00725] 22% S521 S22 [00726] 18% S522 S23 [00727] 23% S523 S24 [00728] 21% S524 S25 [00729] 18% S525 S26 [00730] 19% S526 S27 [00731] 17% S527 S28 [00732] 24% S528 S29 [00733] 25% S529 S30 [00734] 30% S530 S31 [00735] 23% S531 S32 [00736] 25% S532 S33 [00737] 21% S533 S34 [00738] 33% S534 S35 [00739] 24% S535 S36 [00740] 17% S536 S37 [00741] 12% S537 S38 [00742] 14% S538 S39 [00743] 15%

Step 6: Example S600, Symmetrically Substituted Amines

[0258] ##STR00744##

[0259] Variant 1: Buchwald Coupling

[0260] A mixture of 39.6 g (110 mmol) of S500, 4.57 ml (50 mmol) of aniline, 65.2 g (200 mmol) of caesium carbonate, 2.18 g (3.5 mmol) of rac-BINAP [98327-87-8], 561 mg (2.5 mmol) of palladium(II) acetate, 500 ml of toluene and 50 g of glass beads (diameter 3 mm) is stirred first at 60? C. for 4 h and then at 100? C. for 12-16 h. The reaction mixture is allowed to cool to 60? C., and the salts are filtered off through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to dryness, the residue is extracted by boiling with 200 ml of methanol, and the solids are filtered off, washed twice with 50 ml each time of methanol, dried under reduced pressure and subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 21.7 g (39 mmol), 78%; purity: about 95% by .sup.1H NMR.

[0261] Alternatively, it is possible to use other phosphines (e.g. tri-tert-butylphosphine, di-tert-butylmethylphosphine, S-Phos, X-Phos, AmPhos, etc.) and bases (e.g. alkoxides such as sodium tert-butoxide).

[0262] Variant 2: Jourdan-Ullmann Coupling

[0263] A mixture of 39.6 g (110 mmol) of S500, 4.57 ml (50 mmol) of aniline, 27.6 g (200 mmol) of potassium carbonate, 42.7 g (300 mmol) of sodium sulfate, 954 mg (15 mmol) of copper powder, 500 ml of nitrobenzene and 1000 g of glass beads (diameter 3 mm) is stirred first at 160? C. for 12-16 h. The reaction mixture is allowed to cool to 60? C., and the salts are filtered off through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to dryness, the residue is extracted by boiling with 200 ml of methanol, and the solids are filtered off, washed twice with 50 ml each time of methanol, dried under reduced pressure and subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 18.5 g (33 mmol), 65%; purity: about 95% by .sup.1H NMR.

[0264] Analogously, the pyridines S501 to S538 can be reacted with primary arylamines (anilines).

Step 6: Example S700, Asymmetrically Substituted Amines

[0265] ##STR00745##

[0266] A mixture of 18.0 g (50 mmol) of S500, 4.57 ml (50 mmol) of aniline, 65.2 g (200 mmol) of caesium carbonate, 2.18 g (3.5 mmol) of rac-BINAP [98327-87-8], 561 mg (2.5 mmol) of palladium(II) acetate, 500 ml of toluene and 50 g of glass beads (diameter 3 mm) is stirred at 60? C. until conversion is complete (TLC monitoring, typically 2-4 h). Then 11.6 g (50 mmol) of 4-chloro-2,3-dihydro-1H-indene [2402829-95-0] is added and the temperature is increased to 100? C. On completion of conversion (TLC monitoring, typically 12-16 h), the reaction mixture is allowed to cool to 60? C., and the salts are filtered off through a Celite bed in the form of a toluene slurry. The filtrate is concentrated to dryness, the residue is extracted by boiling with 200 ml of methanol, and the solids are filtered off, washed twice with 50 ml each time of methanol, dried under reduced pressure and subjected to flash chromatography (Combi-Flash Torrent from A. Semrau). Yield: 15.3 g (32 mmol), 64%; purity: about 95% by .sup.1H NMR.

[0267] The symmetric and asymmetric amines obtained in this way can be converted as described in C) to the inventive emitters ES and EAS.

[0268] C) Synthesis of the Symmetrically Substituted Emitters:

Step 7: Example ES1

[0269] ##STR00746##

[0270] Variant 1:

[0271] A mixture of 27.8 g (50 mmol) of S600, 27.6 g (200 mmol) of potassium carbonate, 1.72 g (3 mmol) of (NHC)Pd(allyl)Cl [478980-03-9], 50 g of glass beads (diameter 3 mm) and 500 ml of N,N-dimethylacetamide (DMAc) is heated to 150? C. with good stirring for 16 h. After cooling to 80? C., 1000 ml of water is added dropwise, the precipitated solids are filtered off with suction, and these are washed twice with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau, DCM: 2% MeOH), and then purified by repeated hot extraction crystallization (DCM:acetonitrile 1:3 to 2:1) and subsequent fractional sublimation or by heat treatment under high vacuum. Yield: 10.1 g (21 mmol), 42%; purity: >99.9% by HPLC.

[0272] Variant 2:

[0273] A mixture of 27.8 g (50 mmol) S600, 3.1 g (10 mmol) of palladium(II) pivalate [106224-36-6], 27.8 g (120 mmol) of silver(I) oxide [20667-12-3], 9.6 g (120 mmol) of copper(II) oxide [1317-38-0], 50 g of glass beads (diameter 3 mm) and 200 ml of pivalic acid (PivOH) is heated to 130? C. with good stirring for 24 h. After cooling to 80? C., 1000 ml of water is added dropwise, the precipitated solids are filtered off with suction, and these are washed twice with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau, DCM: 2% MeOH), then purified by repeated hot extraction crystallization (DCM:acetonitrile 1:3 to 2:1) and subsequent fractional sublimation or by heat treatment under high vacuum. Yield: 8.5 g (17.5 mmol), 35%; purity: >99.9% by HPLC.

[0274] Analogously to steps 6 and 7, it is possible to prepare the following inventive emitters ES; yield over two steps, (step 6 and 7):

TABLE-US-00013 Pyridine Ex. Amine Product Yield ES2 S500 [00747] 769-92-6 [00748] 35% ES3 S500 [00749] 378723-23-4 [00750] 37% ES4 S500 [00751] 1459-48-9 [00752] 40% ES5 S500 [00753] 91-59-8 [00754] 38% ES6 S500 [00755] 92-67-1 [00756] 35% ES7 S500 [00757] 7293-45-0 [00758] 30% ES8 S500 [00759] 25660-12-2 [00760] 31% ES9 S500 [00761] 76302-58-4 [00762] 37% ES10 S500 [00763] 118951-68-1 [00764] 33% ES11 S500 [00765] 2018346-63-7 [00766] 29% ES12 S500 [00767] 2295808-71-6 [00768] 36% ES13 S500 [00769] 101283-00-5 [00770] 39% ES14 S500 [00771] 1416158-30-9 [00772] 41% ES15 S500 [00773] 129667-70-5 [00774] 26% ES16 S500 [00775] 861046-41-5 [00776] 30% ES17 S500 [00777] 37521-66-7 [00778] 32% ES18 S500 [00779] 1609130-36-0 [00780] 30% ES19 S500 [00781] 13177-26-9 [00782] 25% ES20 S500 [00783] 1639349-82-8 [00784] 34% ES21 S500 [00785] [00786] 33% 2222442-56-8 ES22 S500 [00787] 1882060-04-9 [00788] 38% ES23 S500 [00789] 2379812-68-5 [00790] 36% ES24 S500 [00791] 2086712-51-6 [00792] 36% ES25 S501 [00793] 22948-06-7 [00794] 35% ES26 S502 [00795] 343239-58-7 [00796] 30% ES27 S503 [00797] 1801716-11-9 [00798] 38% ES28 S503 [00799] 1884138-08-2 [00800] 35% ES29 S503 [00801] 31997-11-2 [00802] 36% ES30 S503 [00803] 4106-66-5 [00804] 41% ES31 S503 [00805] 93951-94-1 [00806] 43% ES32 S503 [00807] 37521-64-5 [00808] 39% ES33 S503 [00809] 1846604-58-7 [00810] 27% ES34 S503 [00811] 789-47-9 [00812] 30% ES35 S503 [00813] 1409971-49-8 [00814] 24% ES36 S503 [00815] 2281888-57-9 [00816] 40% ES37 S503 [00817] 1642327-33-0 [00818] 39% ES38 S503 [00819] 2460139-08-4 [00820] 43% ES39 S503 [00821] 2411114-95-7 [00822] 37% ES40 S503 [00823] 2226959-71-1 [00824] 38% ES41 S503 [00825] 122519-95-3 [00826] 40% ES42 S503 [00827] 1448337-95-8 [00828] 29% ES43 S504 [00829] 92-67-1 [00830] 36% ES44A S505 [00831] 108714-73-4 [00832] 13% ES44B [00833] 15% Chromatographic separation of the diastereomers ES45 S506 [00834] 1882060-04-9 [00835] 41% ES46 S507 [00836] 1268519-74-9 [00837] 30% ES47 S508 [00838] 2222442-56-8 [00839] 32% ES48 S509 [00840] 174152-47-7 [00841] 35% ES49 S510 [00842] 1520097-73-7 [00843] 31% ES50 S511 [00844] 25288-76-0 [00845] 36% ES51 S512 [00846] 17169-81-2 [00847] 38% ES51 S513 [00848] 1820037-24-8 [00849] 21% ES53 S514 [00850] 2364548-23-0 [00851] 39% ES54 S515 [00852] 93618-98-5 [00853] 34% ES55 S516 [00854] 3366-65-2 [00855] 19% ES56 S517 [00856] 1093882-02-0 [00857] 39% ES57 S517 [00858] 667919-05-3 [00859] 32% ES58 S520 [00860] 1421789-14-1 [00861] 30% ES59 S521 [00862] 2411114-70-8 [00863] 34% ES60 S522 [00864] 53897-95-3 [00865] 35% ES61 S523 [00866] 118383-59-8 [00867] 37% ES62 S525 [00868] 1853250-47-1 [00869] 35% ES63 S526 [00870] 1117681-08-9 [00871] 26% ES64 S527 [00872] 1644466-73-8 [00873] 40% ES65 S528 [00874] 3693-22-9 [00875] 37% ES566 S529 [00876] 1940112-89-9 [00877] 33% ES67 S530 [00878] 1191512-09-0 [00879] 34% ES68 S531 [00880] 2295808-71-6 [00881] 35% ES69 S533 [00882] 1257982-95-8 [00883] 35% ES70 S534 [00884] 13095-01-6 [00885] 35% ES71 S535 [00886] 2129673-55-6 [00887] 36% ES72 S536 [00888] 2179038-73-2 [00889] 21% ES73 S537 [00890] 1346517-64-3 [00891] 23% ES74 S538 [00892] 1093882-02-0 [00893] 18% ES75 S503 [00894] 43215-86-7 [00895] 31% ES76 [00896] 89167-34-0 [00897] Preparation according to US20150162533 Use of 715-50-4 and 1008788-39-3 [00898] 40% ES200 S503 [00899] 106-50-3 25 mmol [00900] 12% ES201 S513 [00901] 2243-67-6 25 mmol [00902] 24% ES202 S503 [00903] 64535-41-7 25 mmol [00904] 18% ES203 S517 [00905] 866464-33-7 25 mmol [00906] 17% ES204 S500 [00907] 5896-30-0 25 mmol [00908] 20% ES205 S500 [00909] 92-87-5 25 mmol [00910] 24% ES206 S500 [00911] 167559-51-5 25 mmol [00912] 21%

[0275] D) Synthesis of the Asymmetrically Substituted Emitters:

Step 7: Example EAS1

[0276] ##STR00913##

[0277] A mixture of 23.8 g (50 mmol) of S700, 27.6 g (200 mmol) of potassium carbonate, 1.72 g (3 mmol) of (NHC)Pd(allyl)Cl [478980-03-9], 50 g of glass beads (diameter 3 mm) and 500 ml of N,N-dimethylacetamide (DMAc) is heated to 150? C. with good stirring for 16 h. After cooling to 80? C., 1000 ml of water is added dropwise, the precipitated solids are filtered off with suction, and these are washed twice with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau, DCM: 2% MeOH), which also separates isomers that occur. Finally, the emitters thus obtained are purified by repeated hot extraction crystallization (DCM:acetonitrile 1:3 to 2:1) and subsequent fractional sublimation or by heat treatment under high vacuum. Yield: 8.9 g (22 mmol), 44%; purity: >99.9% by HPLC.

[0278] Analogously to steps 6 and 7, it is possible to prepare the following inventive emitters EAS: yield over two steps (step 6 and 7):

TABLE-US-00014 Synthons Ex. Amine Product Yield EAS2A S500 15% [00914] [00915] EAS2B [00916] [00917] 12% EAS2 S500 35% [00918] [00919] [00920] EAS3A S500 18% [00921] [00922] EAS3B [00923] [00924] 15% EAS4A S500 16% [00925] [00926] EAS4B [00927] [00928] 19% EAS5 S503 27% [00929] [00930] [00931] EAS6A S503 13% [00932] [00933] EAS6B [00934] [00935] 17% EAS7 S500 30% [00936] [00937] [00938] EAS8 S500 32% [00939] [00940] [00941] EAS100 S500 30% S517 [00942] [00943] EAS101 S503 34% S520 [00944] [00945] EAS102 S500 31% S503 [00946] [00947] EAS103A S500 18% S503 [00948] [00949] EAS103B [00950] 21% EAS104A S503 S526 [00951] 17% EAS104B [00952] [00953] 15%

[0279] Alternative Synthesis Routes:

[0280] The compounds of the invention, in some cases with improved yields, can be prepared by the following alternative synthesis routes:

[0281] 1) Alternative Method A:

[0282] Stepwise Construction by Two Consecutive Buchwald Couplings, Followed by a Pd-Catalysed Intramolecular Cyclization Using the Example of ES1:

##STR00954##

[0283] Stage 1): Buchwald Coupling 1

##STR00955##

[0284] A mixture of 39.6 g (110 mmol) of S500, 9.13 ml (100 mmol) of aniline [62-53-3], 20.2 g (210 mmol) of sodium tert-butoxide [865-48-5], 1.11 g (2 mmol) of bisdiphenylphosphinoferrocene (dppf) [12150-46-8], 499 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene and 50 g of glass beads (diameter 3 mm) is stirred under gentle reflux until conversion is complete (about 1 h). The reaction mixture is allowed to cool to 60? C., 300 ml of water and 220 ml of 1 N acetic acid are added, and the organic phase is removed and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of a toluene slurry and washed through with 500 ml of ethyl acetate, and the filtrate is concentrated to dryness. The residue is purified by chromatography (silica gel, cyclohexane/EA, Combi-Flash Torrent from A. Semrau). Yield: 30.3 g (93 mmol), 93%; purity: about 97% by .sup.1H NMR.

[0285] Stage 2: Buchwald Coupling 2

##STR00956##

[0286] A mixture of 32.5 g (100 mmol) of stage 1), 39.6 g (110 mmol) of S500, 20.2 g (210 mmol) of sodium tert-butoxide [865-48-5], 725 mg (2.5 mmol) of tri-tert-butylphosphonium tetrafluoroborate [131274-22-1], 449 mg (2 mmol) of palladium(II) acetate, 500 ml of toluene and 50 g of glass beads (diameter 3 mm) is stirred under gentle reflux until conversion is complete (about 12 h). The reaction mixture is allowed to cool to 60? C., 300 ml of water is added, and the organic phase is removed and washed once with 300 ml of water and once with 300 ml of saturated sodium chloride solution and dried over magnesium sulfate. The mixture is filtered through a silica gel bed in the form of a toluene slurry and washed through with 500 ml of ethyl acetate, and the filtrate is concentrated to dryness. The residue is purified by chromatography (silica gel, cyclohexane/EA, Combi-Flash Torrent from A. Semrau). Yield: 48.4 g (87 mmol), 87%; purity: about 97% by .sup.1H NMR.

[0287] Stage 3): Cyclization

[0288] A mixture of 55.7 g (100 mmol) of stage 2), 41.5 g (300 mmol) of potassium carbonate, 725 mg (2.5 mmol) of tri-tert-butylphosphonium tetrafluoroborate [131274-22-1], 449 mg (2 mmol) of palladium(II) acetate, 500 ml of dimethylacetamide and 50 g of glass beads (diameter 3 mm) is stirred at 150? C. until conversion is complete (about 12 h). After cooling to 80? C., 1000 ml of water is added dropwise, the precipitated solids are filtered off with suction, and these are washed twice with 100 ml each time of water and twice with 50 ml each time of methanol, and dried under reduced pressure. The crude product is subjected to flash chromatography (Combi-Flash Torrent from A. Semrau, DCM: 2% MeOH), then purified by repeated hot extraction crystallization (DCM:acetonitrile 1:3 to 2:1) and subsequent fractional sublimation or by heat treatment under high vacuum. Yield: 23.2 g (48 mmol), 48%; purity: >99.9% by HPLC.

[0289] The alternative method A is suitable not just for construction of symmetrically substituted units, but specifically also for construction of asymmetrically substituted emitters, through use of two different halopyridines in stage 1) and stage 2).

[0290] The following compounds can be prepared analogously:

TABLE-US-00015 Pyridine Ex. Amine Product Yield ES77 S501 31% [00957] [00958] ES78 S503 41% [00959] [00960] ES79 S503 38% [00961] [00962] ES80 S525 44% [00963] [00964] ES81 S500 37% [00965] [00966] EAS9A S500 26% S503 [00967] [00968] EAS9B [00969] 9% ES82 S503 40% [00970] [00971] ES83 S504 39% [00972] [00973]

[0291] 2) Alternative Method B:

[0292] Stepwise AminationCyclization Via a Carbazole Intermediate:

##STR00974##

##STR00975##

[0293] The alternative method B is suitable not just for construction of symmetrically substituted units, but specifically also for regiodirectional construction of asymmetrically substituted emitters, through use of two different pyridines in stage 1) and stage 3).

[0294] The following compounds can be prepared analogously:

TABLE-US-00016 Pyridine Ex. Amine Product Yield ES84 [00976] [00977] 36% [00978] EAS10A S403 23% S500 [00979] [00980] EAS10B [00981] 7% ES85 S400 31% S500 [00982] [00983] ES86 S400 33% S500 [00984] [00985] ES87 S400 29% S500 [00986] [00987] ES88 S400 35% S500 [00988] [00989]

[0295] 3) Alternative Method C:

[0296] Construction by Suzuki Coupling of 2,6-bisboranylanilines with the Halopyridines and Subsequent Double Cyclizing Buchwald Amination:

##STR00990##

[0297] The following compounds can be prepared analogously:

TABLE-US-00017 Pyridine Ex. Amine Product Yield ES89 [00991] [00992] 34% [00993] ES90 [00994] [00995] 29% [00996] ES91 [00997] [00998] 26% [00999] ES92 [01000] [01001] 14% [01002]

[0298] 4) Alternative Method D:

[0299] Construction from 3-Fluoro-4-chloropyridines by Suzuki Coupling and Intramolecular Cyclization Via S.sub.N2Ar Reaction:

##STR01003##

[0300] The following compounds can be prepared analogously:

TABLE-US-00018 Pyridine Ex. Amine Product Yield ES93 S425 31% [01004] [01005]

[0301] Measurement of Photoluminescence Spectra (PL Spectra):

[0302] FIG. 1 shows PL spectra of inventive compounds ES1, ES5, ES10 and comp. 661 (see page 170), measured with a Hitachi F-4500 PL spectrometer in about 10.sup.?5 molar degassed toluene solution at room temperature (about 25? C.).

[0303] The PL spectra have very narrow emission bands with low FWHM values (<0.2 eV) and lead to particularly pure-colour emission. Moreover, in the long-wave emission flank, they often have a shoulder or secondary maximum respectively having less than 50% of the intensity of the main maximum. In top-emission OLED components, this leads to a favourably low viewing angle dependence of the colour impression, compared to prior-art narrowband boron-containing emitters that often have no such shoulders or secondary maxima and show greater viewing angle dependence of the colour impression.

[0304] Production of OLED Components

[0305] 1) Vacuum-Processed Components:

[0306] One use of the compounds of the invention is as dopant in the emission layer in fluorescence and hyperfluorescence OLED components.

[0307] OLEDs (organic light emitting diodes) 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).

[0308] 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. After the production, the OLEDs are encapsulated for protection against oxygen and water vapour. The exact layer structure of the electroluminescent OLEDs can be found in the examples. The materials required for production of the OLEDs are shown in table 10.

[0309] 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. The electroluminescent spectra are recorded at a luminance of 100 or 1000 cd/m.sup.2, and these are used to infer the emission colour and the EL-FWHM values (ELectroluminescenceFull Width Half Maximumwidth of the EL emission spectra at half the peak height in eV, for better comparability over the entire spectral range).

[0310] Fluorescence OLED Components:

[0311] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer (EML) always consists of at least one matrix material (host material) SMB and an emitting dopant (emitter) ES or EAS which is added to the matrix material(s) in a particular proportion by volume by co-evaporation. Details given in such a form as SMB:ES or EAS (97:3%) mean here that the material SMB is present in the layer in a proportion by volume of 97% and ES or EAS in a proportion of 3%. Analogously, the electron transport layer may also consist of a mixture of two materials, for example here of ETM1 (50%) and ETM2 (50%); see table 1. The materials used for production of the OLEDs are shown in table 10. The compounds D-Ref.1 to D-Ref.4 (see table 10) are used as a comparison according to the prior art.

[0312] Blue Fluorescence OLED Components BF:

[0313] The OLEDs basically have the following layer structure: [0314] substrate [0315] hole injection layer 1 (HIL1) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0316] hole transport layer 1 (HTL1) composed of HTM1, 160 nm [0317] hole transport layer 2 (HTL2), see table 1 [0318] emission layer (EML), see table 1 [0319] electron transport layer (ETL2), see table 1 [0320] electron transport layer (ETL.sup.1) composed of ETM1 (50%) and ETM2 (50%), 30 nm [0321] electron injection layer (EIL) composed of ETM2, 1 nm [0322] cathode composed of aluminium, 100 nm

TABLE-US-00019 TABLE 1 Structure of blue fluorescence OLED components Ex. HTL2 EML ETL2 Ref-BF1 HTM2 SMB1:Ref.?D1 (97:3%) ETM1 10 nm 20 nm 10 nm Ref-BF2 HTM2 SMB1:Ref.?D2 (97:3%) ETM1 10 nm 20 nm 10 nm Ref-BF3 HTM2 SMB1:Ref.?D3 (97:3%) ETM1 10 nm 20 nm 10 nm Ref-BF4 HTM2 SMB1:Ref.?D4 (97:3%) ETM1 10 nm 20 nm 10 nm BF1 HTM2 SMB1:ES16 (97:3%) ETM1 10 nm 20 nm 10 nm BF2 HTM2 SMB2:ES16 (94:6%) ETM1 10 nm 20 nm 10 nm BF3 HTM2 SMB3:ES40 (97:3%) ETM1 10 nm 20 nm 10 nm BF4 HTM2 SMB3:ES76 (97:3%) ETM1 10 nm 20 nm 10 nm BF5 HTM2 SMB1:ES12 (97:3%) ETM1 10 nm 20 nm 10 nm BF6 HTM2 SMB1:ES17 (97:3%) ETM1 10 nm 20 nm 10 nm BF7 HTM2 SMB1:ES18 (97:3%) ETM1 10 nm 20 nm 10 nm BF8 HTM2 SMB1:ES23 (97:3%) ETM1 10 nm 20 nm 10 nm BF9 HTM2 SMB1:ES23 (97:3%) ETM1 10 nm 20 nm 10 nm BF10 HTM2 SMB1:ES24 (97:3%) ETM1 10 nm 20 nm 10 nm BF11 HTM2 SMB1:ES31 (97:3%) ETM1 10 nm 20 nm 10 nm BF12 HTM2 SMB1:ES32 (97:3%) ETM1 10 nm 20 nm 10 nm BF13 HTM2 SMB1:ES34 (97:3%) ETM1 10 nm 20 nm 10 nm BF14 HTM2 SMB1:ES37 (97:3%) ETM1 10 nm 20 nm 10 nm BF15 HTM2 SMB1:ES38 (97:3%) ETM1 10 nm 20 nm 10 nm BF16 HTM2 SMB1:ES39 (97:3%) ETM1 10 nm 20 nm 10 nm BF17 HTM2 SMB1:ES41 (97:3%) ETM1 10 nm 20 nm 10 nm BF18 HTM2 SMB1:ES56 (97:3%) ETM1 10 nm 20 nm 10 nm BF19 HTM2 SMB1:ES57 (97:3%) ETM1 10 nm 20 nm 10 nm BF20 HTM2 SMB1:ES63 (97:3%) ETM1 10 nm 20 nm 10 nm BF21 HTM2 SMB1:ES64 (97:3%) ETM1 10 nm 20 nm 10 nm BF22 HTM2 SMB1:ES67 (97:3%) ETM1 10 nm 20 nm 10 nm BF23 HTM2 SMB1:EAS3B (97:3%) ETM1 10 nm 20 nm 10 nm BF24 HTM2 SMB1:ES103A (97:3%) ETM1 10 nm 20 nm 10 nm BF25 HTM2 SMB1:ES78 (97:3%) ETM1 10 nm 20 nm 10 nm BF26 HTM2 SMB1:ES82 (97:3%) ETM1 10 nm 20 nm 10 nm BF27 HTM2 SMB1:EAS10A (97:3%) ETM1 10 nm 20 nm 10 nm BF28 HTM2 SMB1:ES92 (95:5%) ETM1 10 nm 20 nm 10 nm

TABLE-US-00020 TABLE 2 Results EQE (%) Voltage (V) EL-FWHM Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 Colour [eV] Ref-BF1 6.3 4.5 blue 0.17 Ref-BF2 0.8 5.2 deep blue 0.22 Ref-BF3 5.5 4.6 blue 0.41 Ref-BF4 3.1 6.8 blue 0.21 BF1 8.3 4.4 blue 0.17 BF2 7.7 4.1 blue 0.17 BF3 8.1 4.3 blue 0.16 BF4 7.6 4.3 blue 0.17 BF5 6.6 4.5 deep blue 0.17 BF6 8.9 4.3 blue 0.18 BF7 8.7 4.4 blue 0.19 BF8 9.1 4.5 blue 0.18 BF9 6.4 4.5 deep blue 0.19 BF10 6.6 4.5 deep blue 0.18 BF11 8.3 4.4 blue 0.17 BF12 8.7 4.6 blue 0.17 BF13 8.3 4.3 blue 0.18 BF14 7.1 4.7 deep blue 0.16 BF15 6.7 4.6 deep blue 0.15 BF16 8.5 4.4 blue 0.17 BF17 8.7 4.5 blue 0.17 BF18 6.9 4.8 deep blue 0.16 BF19 7.0 4.9 blue 0.20 BF20 6.9 4.7 deep blue 0.19 BF21 8.8 4.6 blue 0.20 BF22 8.3 4.6 blue 0.19 BF23 9.1 4.5 blue 0.24 BF24 8.7 4.4 blue 0.18 BF25 8.8 4.5 blue 0.19 BF26 9.0 4.5 blue 0.16 BF27 7.3 4.6 deep blue 0.18 BF28 7.4 4.4 blue 0.21

[0323] Hyperphosphorescence OLED Components:

[0324] All materials are applied by thermal vapour deposition in a vacuum chamber. The emission layer(s) (EML) always consist(s) of at least one matrix material (host material) TMM, a (phosphorescent) sensitizer PS and a fluorescent emitter ES or EAS. The matrix material (host material) TMM may consist of two components that are evaporated as a mixture (premixed host, e.g. TMM2), the components and the composition is likewise shown in table 10. Sensitizers and fluorescent emitter ES or EAS are added to the host material TMM in a particular proportion by volume by coevaporation. Details given in such a form as TMM:PS(5%):ES or EAS(2%) mean here that the material TMM is present in the layer in a proportion by volume of 93%, PS in a proportion of 5% and ES or EAS in a proportion of 2%.

[0325] Blue Hyperphosphorescence OLED Components BH:

[0326] The OLEDs basically have the following layer structure: [0327] substrate [0328] hole injection layer 1 (HIL1) composed of HTM2 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0329] hole transport layer 1 (HTL1) composed of HTM2, 30 nm [0330] hole transport layer 2 (HTL2), see table 3 [0331] emission layer (EML), see table 3 [0332] electron transport layer (ETL2), see table 3 [0333] electron transport layer (ETL.sup.1) composed of ETM1 (50%) and ETM2 (50%), 20 nm [0334] electron injection layer (EIL) composed of ETM2, 1 nm [0335] cathode composed of aluminium, 100 nm

TABLE-US-00021 TABLE 3 Construction of blue hyperphosphorescence OLED components Ex. HTL2 EML ETL2 BH1 HTM3 TMM1:PS1(8%):ES41(2%) ETM3 10 nm 25 nm 10 nm BH2 HTM3 TMM1:PS1(5%):ES41(3%) ETM3 10 nm 25 nm 10 nm BH3 HTM3 TMM1:PS1(5%): ES42(2%) ETM3 10 nm 25 nm 10 nm BH3 HTM3 TMM1:PS1(6%):ES85(3%) ETM3 10 nm 25 nm 10 nm

TABLE-US-00022 TABLE 4 Results EQE (%) Voltage (V) EL-FWHM Ex. 100 cd/m.sup.2 100 cd/m.sup.2 Colour [eV] BH1 13.8 3.4 blue 0.17 BH2 11.3 3.3 blue 0.17 BH3 14.4 3.4 light blue 0.15 BH3 16.1 3.4 blue 0.16

[0336] Green and Yellow Hyperphosphorescence OLED Components GH:

[0337] The OLEDs basically have the following layer structure: [0338] substrate [0339] hole injection layer 1 (HIL1) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0340] hole transport layer 1 (HTL1) composed of HTM1, 30 nm [0341] hole transport layer 2 (HTL2), see table 5 [0342] emission layer (EML), see table 5 [0343] electron transport layer (ETL2), see table 5 [0344] electron transport layer (ETL.sup.1) composed of ETM1 (50%) and ETM2 (50%), 30 nm [0345] electron injection layer (EIL) composed of ETM2, 1 nm [0346] cathode composed of aluminium, 100 nm

TABLE-US-00023 TABLE 5 Construction of green/yellow hyperphosphorescence OLED components Ex. HTL2 EML ETL2 GH1 HTM2 TMM2:PS2(8%):ES201(2%) ETM1 10 nm 20 nm 10 nm GH2 HTM2 TMM2:PS3(10%):ES201(3%) ETM1 10 nm 20 nm 10 nm

TABLE-US-00024 TABLE 6 Results EQE (%) Voltage (V) EL-FWHM Ex. 100 cd/m.sup.2 100 cd/m.sup.2 Colour [eV] GH1 21.4 3.5 yellow- 0.15 green GH2 19.8 3.4 yellow- 0.15 green

[0347] Orange-Red Hyperphosphorescence OLED Components RH:

[0348] The OLEDs basically have the following layer structure: [0349] substrate [0350] hole injection layer 1 (HIL1) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0351] hole transport layer 1 (HTL1) composed of HTM1, 30 nm [0352] hole transport layer 2 (HTL2), see table 7 [0353] emission layer (EML), see table 7 [0354] electron transport layer (ETL2), see table 7 [0355] electron transport layer (ETL.sup.1) composed of ETM1 (50%) and ETM2 (50%), 45 nm [0356] electron injection layer (EIL) composed of ETM2, 1 nm [0357] cathode composed of aluminium, 100 nm

TABLE-US-00025 TABLE 7 Construction of orange-red hyperphosphorescence OLED Ex. HTL2 EML ETL2 RH1 HTM2 TMM2:PS4(10%):ES200(2%) ETM1 10 nm 20 nm 10 nm RH2 HTM2 TMM2:PS4(8%):ES202(1.5%) ETM1 10 nm 20 nm 10 nm

TABLE-US-00026 TABLE 8 Results EQE (%) Voltage (V) EL-FWHM Ex. 100 cd/m.sup.2 100 cd/m.sup.2 Colour [eV] RH1 21.9 3.4 orange-red 0.15 RH2 18.4 3.4 red 0.14

[0358] 2) Solution-Processed Components:

[0359] The production of solution-based OLEDs is fundamentally described in the literature, for example in WO 2004/037887 and WO 2010/097155. The examples that follow combined the two production processes (application from the gas phase and solution processing), such that layers up to and including emission layer were processed from solution and the subsequent layers (hole blocker layer/electron transport layer) were applied by vapour deposition under reduced pressure. For this purpose, the previously described general methods are matched to the circumstances described here (layer thickness variation, materials) and combined as follows.

[0360] The construction used is thus as follows: [0361] substrate [0362] ITO, 50 nm [0363] PEDOT, 20 nm [0364] hole transport layer HIL-Sol, composed of HTM-Sol, 20 nm [0365] emission layer composed of SMB4(97%) and ES(3%) or EAS(3%), 50 nm [0366] electron transport layer (ETL.sup.1) composed of ETM1 (50%) and ETM2 (50%), 25 nm [0367] cathode composed of aluminium, 100 nm

[0368] Substrates used are glass plaques coated with structured ITO (indium tin oxide) of thickness 50 nm. For better processing, these are coated with the buffer (PEDOT) Clevios P VP Al 4083 (Heraeus Clevios GmbH, Leverkusen); PEDOT is at the top. Spin-coating is effected under air from water. The layer is subsequently baked at 180? C. for 10 minutes. The hole transport layer and the emission layer are applied to the glass plates thus coated. The hole transport layer is the polymer HTM-Sol of the structure shown in table 10, which was synthesized according to WO 2010/097155. The polymer is dissolved in toluene, such that the solution typically has a solids content of about 5 g/I when, as is the case here, the layer thickness of 20 nm typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 180? C. for 60 min.

[0369] The emission layer is always composed of at least one matrix material (host material) and an emitting dopant (emitter). Details given in such a form as SMB4 (97%) and ES or EAS (3%) mean here that the material SMB4 is present in the emission layer in a proportion by weight of 97% and the dopant ES or EAS in a proportion by weight of 3%. The mixture for the emission layer is dissolved in toluene or chlorobenzene. The typical solids content of such solutions is about 18 g/I when, as here, the layer thickness of 50 nm which is typical of a device is to be achieved by means of spin-coating. The layers are spun on in an inert gas atmosphere, argon in the present case, and baked at 140 to 160? C. for 10 minutes. The materials used are shown in table 10.

[0370] The materials for the electron transport layer and for the cathode are applied by thermal vapour deposition in a vacuum chamber. The electron transport layer, for example, may consist of more than one material, the materials being added to one another by co-evaporation in a particular proportion by volume. Details given in such a form as ETM1 (50%) and ETM2 (50%) mean here that the ETM1 and ETM2 materials are present in the layer in a proportion by volume of 50% each. The materials used in the present case are shown in table 10.

TABLE-US-00027 TABLE 9 Results for the solution-processed OLEDs at 1000 cd/m.sup.2 EQE Voltage EL-FWHM Ex. Dopant (%) (V) Colour [eV] Sol-BF1 ES17 7.2 4.5 blue 0.18 Sol-BF2 ES86 6.8 4.7 blue 0.17

TABLE-US-00028 TABLE 10 Structural formulae of materials used [01006] [01007] [01008] [01009] [01010] [01011] [01012] [01013] [01014] [01015] [01016] [01017] [01018] [01019] [01020] [01021] [01022] [01023] [01024] [01025] [01026]

[0371] The abbreviations of the inventive compounds that are used in the tables set out above in relation to the OLED components relate to the abbreviations provided in the above synthesis examples.

[0372] By comparison with the references, some of the inventive compounds show narrower electroluminescence spectra, recognizable by the smaller or equal EL-FWHM values (ELectroluminescenceFull Width Half Maximumwidth of the EL emission spectra in eV at half the peak height). Narrower electroluminescence spectra lead to a distinct improvement in colour purity (lower CIE y values). Moreover, EQE values (External Quantum Efficiencies) are distinctly greater and operating voltages are lower compared to the reference, which leads to a distinct improvement in power efficiencies of the device and hence to lower power consumption.

[0373] Production of Components for Colour Conversion

[0374] The compounds of the invention can be used for colour conversion. For this purpose, compounds are incorporated into a composition which is then processed by known methods (spin-coating, slit-coating, screenprinting, nozzle printing, inkjet printing, etc.) to give pixels or two-dimensional layers. The compositions typically consist of crosslinkable components (monomers, oligomers, polymers), for example based on acrylates, acrylamide, polyesters, silicones etc., and one or more thermally or photochemically activatable starter components. It is additionally possible to introduce further components such as organic auxiliaries (antioxidants, stabilizers, levelling aids, viscosity moderators, etc.) or inorganic fillers (SiO.sub.2, TiO.sub.2, Al.sub.2O.sub.3, etc.).

[0375] General Production Procedure for the Composition and Derived Layers:

[0376] 0.5 g of the inventive compound ES or EAS, 0.2 g of titanium dioxide (ToyoColor TiO.sub.2, from Toyo Ink Group) and 10 g of OE-6550 Optical Encapsulant (from Dow Corning) are homogenized at 40? C. with very good stirring (magnetic stirrer) under the action of ultrasound (ultrasound bath). Layers of layer thickness about 15 m are produced by knife-coating and then cured by baking under a nitrogen atmosphere (150? C., 1 hour).

[0377] Spectral Measurement of the Layers:

[0378] Fluorescence spectra and EQE values (external quantum efficiency, EQE=photons emitted/photons absorbed) of the layers are ascertained in a fluorescence spectrometer (C9920, Hamamatsu photonics) with an Ulbricht sphere and fibre optics (excitation wavelength CWL: 450 nm, reference measurement under air at room temperature).

[0379] Results

[0380] Table 11 summarizes the results:

TABLE-US-00029 FWHM EQE Ex. Material Colour [eV] [%] CC1 ES201 yellow-green 0.15 28.9 CC2 ES202 red 0.15 27.8 CC3 EAS104A red 0.15 25.0 CC4 ES204 red 0.19 27.6 CC5 ES19 green 0.22 26.4 CC6 ES42 deep green 0.16 27.4 CC7 ES61 deep green 0.21 28.1 CC8 EAS6A green 0.16 29.1