BORONIC HETEROCYCLIC COMPOUNDS FOR ORGANIC ELECTROLUMINESCENT DEVICES

Abstract

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

Claims

1.-17. (canceled)

18. A compound including at least one structure of the formula (I) ##STR00299## where the further symbols used are as follows: Z.sup.a, Z.sup.b is the same or different at each instance and is N, CR, or the Z.sup.a, Z.sup.b groups form a ring Ar.sup.a, where the ring Ar.sup.a 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 Ar or R.sup.a radicals, where the ring Ar.sup.a together with the CO group and the W.sup.a, W.sup.b groups forms a 5-membered ring; W.sup.a, W.sup.b is the same or different at each instance and is NR, NAr, NB(R).sub.2 or NB(Ar).sub.2, where exactly one of the W.sup.a, W.sup.b groups is NB(R).sub.2, NB(Ar).sub.2, and exactly one of the W.sup.a, W.sup.b groups is NR, NAr, or the W.sup.a, W.sup.b groups form a ring of the formula ##STR00300## where Z.sup.c is R or Ar, the ring Ar.sup.b 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 Ar or R.sup.b radicals, where the ring Ar.sup.b may form a ring system with an R, Ar or Z.sup.c group or the rings Ar.sup.a and Ar.sup.b together may form a ring system, and the dotted lines represent the bonds to the CO group or Z.sup.b 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; the Ar group here may form a ring system with at least one Ar, R, R.sup.a, R.sup.b group or a further group; R, R.sup.a, R.sup.b 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; or heteroarylthio group which has 5 to 60 aromatic ring atoms and may be substituted by one or more R.sup.1 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.1 radicals, or an aralkyl 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.1 radicals; at the same time, two R, R.sup.a, R.sup.b radicals together or with a further group may also 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.

19. A compound as claimed in claim 18, characterized in that the W.sup.a, W.sup.b groups form a ring of the formula ##STR00301## where the symbols Ar.sup.b and Z.sup.c have the definition given above.

20. A compound as claimed in claim 18, including at least one structure of the formula (II-1) to (II-18): ##STR00302## ##STR00303## where the symbols R, Ar, Ar.sup.a and Ar.sup.b have the definitions given in claim 18 and X is the same or different at each instance and is N or CR.

21. A compound as claimed in claim 18, comprising at least one structure of the formulae (III-1) to (III-48): ##STR00304## ##STR00305## ##STR00306## ##STR00307## ##STR00308## ##STR00309## ##STR00310## ##STR00311## ##STR00312## ##STR00313## where the symbols Ar and R have the definitions given in claim 18 and the further symbols are as follows: X is the same or different at each instance and is N or CR, with the proviso that not more than two of the X groups in one cycle are N, where R has the definition detailed in claim 18; X.sup.a is the same or different at each instance and is N or CR.sup.a, with the proviso that not more than two of the X.sup.a groups in one cycle are N, where R.sup.a has the definition detailed in claim 18; X.sup.b is the same or different at each instance and is N or CR.sup.b, with the proviso that not more than two of the X.sup.b groups in one cycle are N, where R.sup.b has the definition detailed in claim 18, Y.sup.1 is the same or different at each instance and 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; Y.sup.2 is the same or different at each instance and 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; Y.sup.3 is the same or different at each instance and is 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; Y.sup.4 is the same or different at each instance and is N(Ar), N(R), P(Ar), P(R), P(O)Ar, P(O)R, P(S)Ar, P(S)R, C(R).sub.2, Si(R).sub.2, O or S, where R has the definition detailed in claim 18; Y.sup.5 is the same or different at each instance and is 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; Y.sup.6 is the same or different at each instance and is 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18.

22. A compound as claimed in claim 18, comprising at least one structure of the formulae (IV-1) to (IV-48): ##STR00314## ##STR00315## ##STR00316## ##STR00317## ##STR00318## ##STR00319## ##STR00320## ##STR00321## ##STR00322## ##STR00323## where the symbols R, R.sup.a and R.sup.b have the definitions given in claim 18, and the further symbols are as follows: Y.sup.1 is the same or different at each instance and 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; Y.sup.2 is the same or different at each instance and 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; Y.sup.3 is the same or different at each instance and is 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; Y.sup.4 is the same or different at each instance and is N(Ar), N(R), P(Ar), P(R), P(O)Ar, P(O)R, P(S)Ar, P(S)R, C(R).sub.2, Si(R).sub.2, O or S, where R has the definition detailed in claim 18; Y.sup.5 is the same or different at each instance and is 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; Y.sup.6 is the same or different at each instance and is 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, Ge(R).sub.2, CNR, CNAr, CC(R).sub.2, CC(R)(Ar), O, S, Se, SO, or SO.sub.2, where R has the definition detailed in claim 18; m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; j is 0, 1 or 2; k is 0 or 1.

23. A compound as claimed in claim 18, characterized in that the structures/compounds of the formulae (I), (II-1) to (II-18), (III-1) to (III-48) and/or (IV-1) to (IV-48) have not more than one olefinic double bond.

24. A compound as claimed in claim 18, characterized in that at least two R, R.sup.a, R.sup.b radicals together with the further groups to which the two R, R.sup.a, R.sup.b radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b radicals form at least one structure of the formulae (RA-1) to (RA-12): ##STR00324## ##STR00325## 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.b radicals bind, and the further symbols are defined as follows: Y.sup.7 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), NR.sup.1, NAr, O or S; R.sup.c 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 R.sup.c radicals together or one R.sup.c radical together with an R.sup.1 radical or together with a further group 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.

25. A compound as claimed in claim 18, characterized in that at least two R, R.sup.a, R.sup.b radicals together with the further groups to which the two R, R.sup.a, R.sup.b radicals bind form a fused ring, where the two R, R.sup.a, R.sup.b radicals of the form structures of the formula (RB): ##STR00326## where R.sup.1 has the definition detailed in claim 18, the dotted bonds represent the sites of attachment via which the two R, R.sup.a, R.sup.b, R.sup.c, R.sup.d radicals bind to the further groups, the index m is 0, 1, 2, 3 or 4 and Y.sup.8 is C(R.sup.1).sub.2, NR.sup.1, NAr, BR.sup.1, BAr, O or S.

26. A compound as claimed in claim 18, comprising at least one structure of the formulae (V-1) to (V-12), where the compounds have at least one fused ring, ##STR00327## ##STR00328## ##STR00329## where the symbols R.sup.a, R.sup.b, Y.sup.1, Y.sup.2 and Y.sup.5 have the definitions given in claim 18, the symbol o represents the sites of attachment, and the further symbols have the following definition: m is 0, 1, 2, 3 or 4; n is 0, 1, 2 or 3; j is 0, 1 or 2.

27. A compound as claimed in claim 18, characterized in that at least one substituent R, R.sup.a, R.sup.b is the same or different at each instance and is selected from the group consisting of H, D, a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 carbon atoms or an aromatic or heteroaromatic ring system selected from the groups of the following formulae Ar-1 to Ar-78: ##STR00330## ##STR00331## ##STR00332## ##STR00333## ##STR00334## ##STR00335## ##STR00336## ##STR00337## ##STR00338## ##STR00339## ##STR00340## ##STR00341## ##STR00342## ##STR00343## ##STR00344## ##STR00345## ##STR00346## where R.sup.1 has the definitions given above, the dotted bond represents the bond to the corresponding group and in addition: Ar.sup.1 is the same or different at each instance and is a bivalent aromatic or heteroaromatic ring system which has 6 to 18 aromatic ring atoms and may be substituted in each case by one or more R.sup.1 radicals; A is the same or different at each instance and is C(R.sup.1).sub.2, NR.sup.1, O or S; p is 0 or 1, where p=0 means that the Ar.sup.1 group is absent and that the corresponding aromatic or heteroaromatic group is bonded directly to the corresponding radical; q is 0 or 1, where q=0 means that no A group is bonded at this position and R.sup.1 radicals are bonded to the corresponding carbon atoms instead.

28. A compound as claimed in claim 18, characterized in that the compound includes exactly two or exactly three structures of formula (I), (II-1) to (II-18), (III-1) to (III-48), (IV-1) to (IV-48) and/or (V-1) to (V-12).

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

30. A formulation comprising at least one compound as claimed in claim 18 and at least one further compound, where the further compound is selected from one or more solvents.

31. A composition comprising at least one compound as claimed in claim 18 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.

32. A process for preparing a compound as claimed in claim 18, characterized in that a base skeleton having at least one of the W.sup.a groups or a precursor of one of the W.sup.a groups is synthesized, and an aromatic or heteroaromatic radical is introduced by means of a nucleophilic aromatic substitution reaction or a coupling reaction.

33. A method for making an electronic device comprising the use of a compound as claimed in claim 18.

34. An electronic device comprising at least one compound as claimed in claim 18.

Description

EXAMPLES

[0203] 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.

Synthons Known from the Literature:

##STR00147## ##STR00148##

Synthesis of Synthons S

Example B1

##STR00149##

Stage A):

##STR00150##

[0204] Synthesis analogous to V. Bodmer-Narkevitch et al., Bioorg. Med. Chem. Lett. 2010, (20) 7011. A mixture of 37.1 g (100 mmol) of 3-iodophenyidiphenylamine [1287245-66-2], 14.8 g (110 mmol) of indazolinone, LS1 [7364-25-2], 68.2 g (220 mmol) of tripotassium phosphate, 952 mg (5 mmol) of copper iodide, 1.14 g (10 mmol) of rac-trans-1,2-diaminocyclohexane [1121-22-8], 100 g of glass beads (diameter 3 mm) and 500 ml of dioxane is heated under reflux for 24 h. The mixture is filtered while still hot through a Celite bed in the form of a dioxane slurry, the filtrate is concentrated under reduced pressure, and the residue is taken up in 500 ml of dichloromethane (DCM), washed three times with 200 ml of 5% aqueous EDTA solution and once with 300 ml of saturated sodium chloride solution, and dried over magnesium sulfate. The desiccant is filtered off by means of a silica gel bed in the form of a DCM slurry, and the filtrate is concentrated gradually under reduced pressure, while continuously replacing the DCM distilled off with 100 ml of methanol. The crystallized product is filtered off with suction, washed twice with 50 ml each time of methanol and dried under reduced pressure. Purification is effected by flash chromatography (CombiFlash Torrent automated column system from A. Semrau, silica gel, cyclohexane/ethyl acetate (EA)). Yield: 20.5 g (54 mmol), 54%; purity: about 98% by .sup.1H NMR.

Stage B): B1

[0205] Added dropwise to a well-stirred suspension, cooled to 78 C., of 18.9 g (50 mmol) B1 of stage A) in 300 ml of toluene is 31.3 ml (50 mmol) of n-BuLi (1.6 M in n-hexane), the mixture is stirred for 30 min, then allowed to warm up to 0 C. over the course of 30 min, stirred for another 30 min and cooled again to 78 C. With very good stirring, 50 ml (50 mmol) of boron trichloride 1 N in n-heptane is added dropwise, the mixture is allowed to warm up to room temperature and stirred for another 1 h, and the solvent is removed under reduced pressure. The residue is taken up in 300 ml of o-dichlorobenzene, 18.7 ml (110 mmol) of 2,2,6,6-tetramethylpiperidine and 40.0 g (300 mmol) of aluminum trichloride, anhydrous, are added and the mixture is stirred at 150 C. for 20 h. After cooling, a mixture of 29.6 ml (300 mmol) of 1,4-diazabicyclo[2.2.2.]octane and 100 ml of o-dichlorobenzene is added, the mixture is stirred for another 1 h, filtered through a Celite bed in the form of an o-dichlorobenzene slurry and washed through with o-dichlorobenzene, and the filtrate is concentrated to dryness. Further purification is effected by continuous hot extraction (standard organic solvents or a combination thereof, preferably acetonitrile/DCM 3:1 to 1:3) or by flash chromatography (CombiFlash Torrent automated column system from A. Semrau, silica gel, RP silica gels, aluminum oxide, eluent: toluene/n-heptane/triethylamine, acetonitrile/THF or DCM) and final fractional sublimation or heat treatment under high vacuum (typically T about 200-400 C., p about 10.sup.5 to 10.sup.6 mbar). Yield: 3.2 g (8.3 mmol), 16.6%; purity: about 99.9% by .sup.1H NMR.

[0206] The following compounds can be prepared analogously:

TABLE-US-00002 Ex. Reactant Product Yield B2 [00151] [00152] 20% 1287245-66-2 LS12 B3 [00153] [00154] 18% 1801609-87-9 LS5 B4 [00155] [00156] 21% 1825341-72-7 LS3 B5 [00157] [00158] 16% 1306616-39-6 LS2 B6 [00159] [00160] 17% 1306616-38-5 LS7 B7 [00161] [00162] 15% 1357572-67-8 LS4 B8 [00163] [00164] 19% 1686100-23-1 LS11 B9 [00165] [00166] 15% 1705586-11-7 LS9 B10 [00167] [00168] 14% 1689530-24-2 LS8 B11 [00169] [00170] 16% 1689530-26-4 LS5 B12 [00171] [00172] 20% 2598066-40-9 LS3 B13 [00173] [00174] 19% 1644466-58-9 LS5 B14 [00175] [00176] 22% 1537218-86-2 LS5 B15 [00177] [00178] 17% 2252311-13-8 LS3 B16 [00179] [00180] 17% 1613370-82-3 LS5 B17 [00181] [00182] 19% 834600-31-5 LS12 B18 [00183] [00184] 2088740-35-4 LS13 B19 [00185] [00186] 16% 1320278-50-9 LS3 B20 [00187] [00188] 18% 1801610-95-6 LS5 B21 [00189] [00190] 20% 2396477-58-8 LS3 B22 [00191] [00192] 12% 2558183-01-8 LS3 B23 [00193] [00194] 21% 2086293-14-1 LS5 B24 [00195] [00196] 14% 2639695-70-6 LS3 B25 [00197] [00198] 19% 185112-62-2 LS5 B26 [00199] [00200] 11% 1353573-69-9 LS3 B27 [00201] [00202] 18% 2152624-01-4 LS3 B28 [00203] [00204] 18% 750573-24-1 LS3 B29 [00205] [00206] 17% 1699755-95-7 LS5 B30 [00207] [00208] 24% 1313412-22-4 LS3 B31 [00209] [00210] 16% 2134579-54-5 LS3 B32 [00211] [00212] 13% 345924-30-3 LS5 B33 [00213] [00214] 15% 2408582-90-9 LS12 B34 [00215] [00216] 20% 2098479-76-4 LS5 B35 [00217] [00218] 16% 6876-00-2 LS7 B36 [00219] [00220] 18% 2053644-32-7 LS5 B37 [00221] [00222] 17% 2440166-44-7 LS3 B38 [00223] [00224] 17% 2440166-46-9 LS3 B39 [00225] [00226] 21% 1894186-07-2 LS5 B40 [00227] [00228] 16% 2242423-27-2 LS5 B41 [00229] [00230] 13% 1579852-37-1 LS3 B42 [00231] [00232] 9% 52089-10-8 LS6 B43 [00233] [00234] 13% 2648147-34-4 LS6 B44 [00235] [00236] 15% 1257251-75-4 LS6 B45 [00237] [00238] 12% 2416771-53-2 LS5 B46 [00239] [00240] 17% 2416771-62-3 LS5 B47 [00241] [00242] 14% 1609484-24-3 LS6 B48 [00243] [00244] 25% 108-36-1 50 mmol in stage A) LS3 Use of 25 mmol of stage A) in stage B) B49 [00245] [00246] 20% 1680203-50-2 50 mmol in stage A) LS5 Use of 25 mmol of stage A) in stage B) B50 [00247] [00248] 19% 2059982-89-5 50 mmol in stage A) LS3 Use of 25 mmol of stage A) in stage B) B51 [00249] [00250] 24% 750573-26-3 50 mmol in stage A) LS10 Use of 25 mmol of stage A) in stage B)

Example B100

##STR00251##

Stage A):

##STR00252##

[0207] Preparation analogous to K. J. Wicht et al., J. Med. Chem. 2016, 59, 6512. Added dropwise to a well-stirred solution, cooled to 0 C., of 1.85 g (10 mmol) of 3-phenoxyaniline [3586-12-7] in a mixture of 50 ml of DCM and 10 ml of pyridine is a solution of 1.86 g (10 mmol) of 2-nitrobenzoyl chloride [610-14-0] in 50 ml of DCM. The reaction mixture is allowed to warm up to room temperature and stirred until conversion is complete (about 6 h). The reaction mixture is poured on to 200 ml of ice water, and the organic phase is separated off, washed twice with 100 ml each time of water and once with 100 ml of saturated sodium chloride solution, and dried over sodium sulfate. The desiccant is filtered off, the filtrate is concentrated under reduced pressure, and the residue is subjected to hot extraction by stirring with 30 ml of methanol. Yield: 3.0 g (9.0 mmol), 90%; purity: about 97% by .sup.1H NMR.

Stage B): B100

##STR00253##

[0208] Procedure analogous to Y. Bao et al., Org. Lett. 2020, 22, 6277. Added dropwise to a well-stirred mixture, cooled to 0 C., of 3.34 g (10 mmol) of 2-nitro-N-(3-phenoxyphenyl)benzamide [1286040-75-2] stage A), 4.48 g (50 mmol) of tetrahydroxydiboron [13675-18-8] and 150 ml of methanol is a solution of 2.40 g (100 mmol) of NaOH in a mixture of 140 ml of methanol and 10 ml of water. The mixture is stirred at 0 C. for a further 30 min, then allowed to warm up to room temperature and stirred at 40 C. for a further 16 h. Then 200 ml of 0.5 N aqueous acetic acid is added dropwise and the mixture is concentrated under reduced pressure to about 100 ml. The precipitated product is filtered off, washed three times with 30 ml each time of water and twice dried azeotropically with 100 ml each time of toluene, and residues of toluene are removed by drying under reduced pressure. Yield: 2.54 g (8.4 mmol), 84%; purity: about 98% by .sup.1H NMR.

C) B100

[0209] Procedure analogous to examples B1 stage B). Starting materials: 3.02 g (10 mmol) of stage B). Yield: 440 mg (1.41 mmol), 14%; purity: about 99.9% by .sup.1H NMR.

[0210] The following compounds can be prepared analogously:

TABLE-US-00003 Ex. Reactant Product Yield B101 [00254] [00255] 19% 1030588-95-4 from stage B) B102 [00256] [00257] 15% 129951-46-8 [00258] 887580-43-0 B103 [00259] [00260] 10% 610-14-0 [00261] 625107-12-2 B104 [00262] [00263] 18% 832151-90-3 [00264] 116724-06-2 B105 [00265] [00266] 17% 832151-90-3 [00267] 2222100-10-7 B106 [00268] [00269] 15% 99847-46-8 [00270] 58737-02-3 B107 [00271] [00272] 21% 99847-46-8 [00273] 2459228-95-4 B108 [00274] [00275] 11% 832151-90-3 [00276] 3985-12-4 B109 [00277] [00278] 12% 99847-46-8 [00279] 58736-39-3 B110 [00280] [00281] 10% 99847-46-8 [00282] 1786434-59-0 B111 [00283] [00284] 8% 99847-46-8 [00285] 114999-33-6 B112 [00286] [00287] 12% 610-14-0 [00288] 866362-01-8 5 mmol in stage A) Use of 5 mmol of stage A) in stage B)

Example: Production of the OLEDs

1) Vacuum-Processed Devices:

[0211] 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).

[0212] 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.

1a) Blue and Green Fluorescence OLED ComponentsBF and GF:

[0213] All materials are applied by thermal vapor deposition in a vacuum chamber. The emission layer (EML) here always consists of at least one matrix material (host material) SMB (see table 1) and an emitting dopant (dopant, emitter) B, 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:B (97:3%) mean here that the material SMB is present in the layer in a proportion by volume of 97% and the dopant B in a proportion of 3%. Analogously, the electron transport layer may also consist of a mixture of two materials; see table 1. The materials used for production of the OLEDs are shown in table 5.

[0214] 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) as a function of luminance, calculated from current-voltage-luminance characteristics (IUL characteristics) assuming Lambertian emission characteristics, and also the lifetime are determined. Electroluminescence spectra are determined at a luminance of 1000 cd/m.sup.2, and these are used to determine the color and the FWHM (full width at half maximum).

[0215] The OLEDs have the following layer structure: [0216] Substrate [0217] Hole injection layer 1 (HIL1) composed of HTM1 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0218] Hole transport layer 1 (HTL1) composed of HTM1, 140 nm [0219] Hole transport layer 2 (HTL2) composed of HTM2, 10 nm [0220] Emission layer (EML), see table 1 [0221] Electron transport layer (ETL2), see table 1 [0222] Electron transport layer (ETL1), see table 1

TABLE-US-00004 TABLE 1 Structure of blue and green fluorescent OLED components Ex. EML ETL2 ETL1 BF1 SMB1:B3 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF2 SMB2:B5 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF3 SMB3:B8 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF4 SMB1:B14 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF5 SMB1:B16 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF6 SMB1:B23 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF7 SMB1:B24 (97:3%) ETM1 ETM1:ETM2 (50:50%) 20 nm 5 nm 30 nm BF8 SMB1:B26 (97:3%) ETM1 ETM1:ETM2 (50:50%) 20 nm 5 nm 30 nm BF9 SMB1:B28 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF10 SMB1:B33 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF11 SMB1:B35 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF12 SMB1:B45 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF13 SMB1:B48 (95:5%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF14 SMB1:B51 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm BF15 SMB1:B107 (97:3%) ETM1:ETM2 (60:40%) 20 nm 30 nm GF1 SMB1:B7 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm GF2 SMB1:B12 (97:3%) ETM1:ETM2 (50:50%) 20 nm 30 nm Electron injection layer (EIL) composed of ETM2, 1 nm Cathode composed of aluminum, 100 nm

TABLE-US-00005 TABLE 2 Results for blue (420-499 nm) and green (500-540 nm) fluorescent OLED components EQE (%) Voltage [V] Ex. 1000 cd/m.sup.2 1000 cd/m.sup.2 Color FWHM [eV] BF1 8.8 3.7 blue 0.20 BF2 7.9 3.6 blue 0.16 BF3 7.7 3.5 blue 0.17 BF4 7.2 3.7 blue 0.22 BF5 8.5 3.5 blue 0.18 BF6 8.3 3.7 blue 0.16 BF7 8.8 3.5 blue 0.16 BF8 8.6 3.5 blue 0.15 BF9 9.1 3.8 blue 0.16 BF10 7.9 3.6 blue 0.18 BF11 8.4 3.8 blue 0.16 BF12 8.1 3.6 blue 0.17 BF13 8.8 3.8 blue 0.21 BF14 9.4 3.6 blue 0.19 BF15 7.0 3.7 blue 0.24 GF1 9.1 3.3 green 0.23 GF2 10.3 3.3 green 0.20

1 b) Hyperphosphorescent OLED Components:

[0223] All materials are applied by thermal vapor 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 B. Sensitizer PS and fluorescent emitter B are added to the host material TMM in a particular proportion by volume by coevaporation. Details given in such a form as TMM:PS(8%):B(1%) mean here that the material TMM is present in the layer in a proportion by volume of 91%, PS in a proportion of 8% and fluorescent emitter B in a proportion of 1%.

Blue Hyperphosphorescence OLED Components BH:

[0224] The OLEDs basically have the following layer structure: [0225] Substrate [0226] Hole injection layer 1 (HIL1) composed of HTM2 doped with 5% NDP-9 (commercially available from Novaled), 20 nm [0227] Hole transport layer 1 (HTL1) composed of HTM2, 30 nm [0228] Hole transport layer 2 (HTL2), see table 3 [0229] Emission layer (EML), see table 3 [0230] Electron transport layer (ETL2), see table 3 [0231] Electron transport layer (ETL1) composed of ETM1 (50%) and ETM2 (50%), 20 nm [0232] Electron injection layer (EIL) composed of ETM2, 1 nm [0233] Cathode composed of aluminum, 100 nm

TABLE-US-00006 TABLE 3 Construction of blue hyperphosphorescence OLED components Ex. HTL2 EML ETL2 BH1 HTM3 TMM1:PS1(8%):B21(1%) ETM3 10 nm 25 nm 10 nm BH2 HTM3 TMM1:PS1(8%):B34(1%) ETM3 10 nm 25 nm 10 nm

TABLE-US-00007 TABLE 4 Results EQE (%) Voltage (V) EL-FWHM Ex. 100 cd/m.sup.2 100 cd/m.sup.2 Color [eV] BH1 15.9 3.6 blue 0.23 BH2 17.0 3.7 blue 0.19

TABLE-US-00008 TABLE 5 Structural formulae of the materials used [00289] HTM1 136463-07-5 [00290] HTM2 1450933-44-4 [00291] HTM3 1206465-62-4 [00292] TMM1 = ETM3 1201800-83-0 [00293] SMB1 [1087346-88-0] [00294] SMB2 [667940-34-3] [00295] SMB3 [1627916-48-6] [00296] PS1 1541114-98-0 [00297] ETM1 1233200-52-6 [00298] ETM2 25387-93-3

[0234] The abbreviations shown in tables 1 and 3 in relation to the materials of the invention, for example B3, B5, B7, B8, B12, B14, B16, B21, B34, B23, B24, B26, B28, B33, B35, B45, B48, B51 and B107 etc., relate to the compounds set out in detail above in the synthesis examples.

[0235] The compounds of the invention shown narrow electroluminescence spectra, recognizable by the relatively small EL-FWHM values (ELectroluminescenceFull Width Half Maximumwidth of the EL emission spectra in eV at half the peak height). Narrow electroluminescence spectra lead to a distinct improvement in color purity (lower CIE y values). Moreover, very good EQE values (External Quantum Efficiencies) are achieved at low operating voltages, which leads to a distinct improvement in power efficiencies of the device and hence to lower power consumption.