BENZIMIDAZOLO[1,2-A]BENZIMIDAZOLE DERIVATIVES FOR ORGANIC LIGHT EMITTING DIODES

Abstract

Compounds of formula (I) and their use in electronic devices, especially electroluminescent devices: (I) wherein at least two of the substituents R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, R.sup.6 and R.sup.7, or R.sup.7 and R.sup.8 form together one of the following ring systems (IIa), (IIb) (IIc). When used as charge transport material, charge blocker material and/or host material in electroluminescent devices, the compounds of formula (I) may provide improved efficiency, stability, manufacturability, or spectral characteristics of electroluminescent devices and reduced driving voltage of electroluminescent devices.

##STR00001##

Claims

1: A compound of formula (I): ##STR01664## wherein: at least two of the substituents R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, R.sup.6 and R.sup.7, or R.sup.7 and R.sup.8 form together one of the following ring systems: ##STR01665## X is NR.sup.19, O, S, C(R.sup.28).sub.2, or Si(R.sup.28).sub.2; R.sup.9 and R.sup.19 are independently of each other group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.20; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.20 or a group E, or adjacent groups R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, R.sup.6 and R.sup.7, and/or R.sup.7 and R.sup.8 can from together a ring; R.sup.10, R.sup.11, R.sup.12, R.sup.13 are independently of each other H, CN or group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.20 or a group E, or adjacent groups R.sup.10 and R.sup.11, R.sup.11 and R.sup.12 and/or R.sup.12 and R.sup.13 can from together a ring; o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0; o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0, or 1, A.sup.1, A.sup.2, A.sup.3, A.sup.4 are independently of each other a C.sub.6-C.sub.24 arylene group which is unsubstituted or substituted by G, C.sub.2-C.sub.24 heteroarylene group which is unsubstituted or substituted by G; R.sup.20 is a C.sub.6-C.sub.30 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.60 heteroaryl group which is unsubstituted or substituted by G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D, or, in the case that at last one of o, p, q and r is 1, R.sup.20 is CN; A.sup.1, A.sup.2, A.sup.3, A.sup.4 are independently of each other a C.sub.6-C.sub.24 arylene group which is unsubstituted or substituted by G, C.sub.2-C.sub.24 heteroarylene group which is unsubstituted or substituted by G; R.sup.20 is H, CN, a C.sub.6-C.sub.30 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.60 heteroaryl group which is unsubstituted or substituted by G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; R.sup.28 is independently of each other C.sub.6-C.sub.18aryl which is unsubstituted or substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; or C.sub.1-C.sub.18alkyl which is interrupted by O, which is unsubstituted or substituted by E, or two residues R.sup.28 can together with the carbon atom or Si atom to which they are bonded form a ring; D is CO, COO, S, SO, SO.sub.2, O, -CR.sup.63CR.sup.64, NR.sup.65, SiR.sup.70R.sup.71, POR.sup.72, or CC; E is OR.sup.69, SR.sup.69, NR.sup.65R.sup.66, COR.sup.68, COOR.sup.67, CONR.sup.65R.sup.66, CN, Si(R.sup.70).sub.3 or halogen; G is E, or a C.sub.1-C.sub.24alkyl group, a C.sub.6-C.sub.24aryl group, a C.sub.6-C.sub.24aryl group, which is substituted by F, C.sub.1-C.sub.24alkyl, C.sub.1-C.sub.24alkyl which is interrupted by O, a C.sub.2-C.sub.30heteroaryl group, or a C.sub.2-C.sub.30heteroaryl group, which is substituted by F, C.sub.1-C.sub.24alkyl, C.sub.1-C.sub.24alkyl which is interrupted by O; R.sup.63 and R.sup.64 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O; R.sup.65 and R.sup.66 are independently of each other a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O, or R.sup.65 and R.sup.66 together form a five or six membered ring; R.sup.67 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.68 is H; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.69 is a C.sub.6-C.sub.18aryl; a C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.70 and R.sup.71 are independently of each other a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; and R.sup.72 is a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; wherein the dotted lines are bonding sites.

2: The compound of formula (I) as claimed in claim 1, wherein X is NR.sup.19 or C(R.sup.28).sub.2.

3: The compound of formula (I) as claimed in claim 1, wherein two of the substituents R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, R.sup.6 and R.sup.7, or R.sup.7 and R.sup.8 form together a ring system of formula IIa, IIb or IIc.

4: The compound of formula (I) as claimed in claim 1, wherein: at least two of the substituents R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, or R.sup.6 and R.sup.7form together a ring system of formula IIa, IIb or IIc, preferably a ring system of formula IIa or IIb; or at least two of the substituents R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, R.sup.6 and R.sup.7, or R.sup.7 and R.sup.8 form together a ring system of formula (IIc).

5: The compound of formula (I) as claimed in claim 4, having the formula (I-IIb), (I-IIb), (I-IIc), (I-IIc), (I-IIc), (I-IIc), (I-IIca), (I-IIca), (I-IIca), (I-IIca), (I-IIcb), (I-IIcb), (I-IIcb), (I-IIcb), (I-IIcb), (I-IIcb), (I-IIcb), (I-IIcb), (I-IIca), (I-IIca), (I-IIca), (I-IIca), (I-IIca) or (I-IIca: ##STR01666## ##STR01667## ##STR01668## ##STR01669## ##STR01670## wherein R.sup.1 and R.sup.4 and R.sup.5 and R.sup.8.

6: The compound of formula (I) as claimed in claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8, which are not forming together a ring system of formula IIa, IIb or IIc are H, or one of R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is CN and/or a C.sub.6-C.sub.18 aryl group which is unsubstituted or substituted G, a C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D, and all other R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are H; or R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or one of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 is a C.sub.6-C.sub.18 aryl group which is unsubstituted or substituted G, a C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted G or a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and/or interrupted by D, and all other R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are H.

7: The compound of formula (I) as claimed in claim 1, wherein R.sup.10, R.sup.1, R.sup.12 and R.sup.13 are H, or one of R.sup.10, R.sup.11, R.sup.12 and R.sup.13 is CN and/or a C.sub.6-C.sub.18 aryl group which is unsubstituted or substituted G, a C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D, and all other R.sup.10, R.sup.1, R.sup.12 and R.sup.13 are H.

8: The compound of formula (I) as claimed in claim 1, wherein A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.1, A.sup.2, A.sup.3 and A.sup.4 are independently of each other a group of the following formula: ##STR01671## which can be unsubstituted or substituted by G whereby G is defined above; R.sup.73 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.38 a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; a C.sub.6-C.sub.24aryl group, which can optionally be substituted by G, or a C.sub.1-C.sub.24heteroaryl group, which can optionally be substituted by G; and/or two adjacent groups of the groups may form together with the atom to which they are bonded a ring structure, which can optionally be substituted by G; R.sup.130 is independently in each occurrence H or C.sub.6-C.sub.24arylene group, which can optionally be substituted by G, or a C.sub.2-C.sub.30heteroarylene group, which can optionally be substituted by G; wherein G is as defined in above; wherein the dotted lines are bonding sites; wherein (C) has the meaning that the bonding site of the group A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.1, A.sup.2, A.sup.3 and A.sup.4 is linked to a C-atom, and (N) has the meaning that the bonding site of the group A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.1, A.sup.2, A.sup.3 and A.sup.4 is linked to a N-atom, and (C,N) has the meaning that the bonding site of the group A.sup.1, A.sup.2, A.sup.3, A.sup.4, A.sup.1, A.sup.2, A.sup.3 and A.sup.4 is linked to a C or N-atom.

9: The compound of formula (I) as claimed in claim 1, wherein R.sup.20 is H, CN or a group of the following formula and R.sup.20 is independently of R.sup.20 a group of the following formula: ##STR01672## or, in the case that at last one of o, p, q and r is 1, CN; wherein: X.sup.1 is S, O, C(R.sup.21).sub.2, NR.sup.23; R.sup.22 is a C.sub.6-C.sub.18 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted by G; R.sup.23 is H, a C.sub.6-C.sub.18 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted by G; R.sup.24 and R.sup.25 are independently of each other H, a C.sub.6-C.sub.18 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted by G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D, or CN; a is 0, 1, 2 or 3; b is 0, 1, 2, 3 or 4; the dotted lines are bonding sites; or ##STR01673## wherein: X.sup.1, X.sup.2 and X.sup.3 are independently of each other CR.sup.16 or N, wherein in formula (8) at least one of X.sup.1 to X.sup.3 is N, and wherein in formulae (9) and (10) at least one of X.sup.1 and X.sup.3 is N; Ar.sub.1 and Ar.sub.2 are independently of each other a C.sub.6-C.sub.24 aryl group, which is optionally substituted by G, or a C.sub.1-C.sub.24 heteroaryl group, which is optionally substituted by G; R.sup.16, R.sup.17 and R.sup.18 are independently of each other H, a C.sub.6-C.sub.24 aryl group which can be substituted by G, a C.sub.1-C.sub.24 heteroaryl group which can be substituted by G or a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and/or interrupted by D; or ##STR01674## ##STR01675## R.sup.26, R.sup.27, R.sup.28 and R.sup.29 are independently of each other H, a C.sub.6-C.sub.24 aryl group which can be substituted by G, a C.sub.1-C.sub.24 heteroaryl group which can be substituted by G or a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and/or interrupted by D; or a substituent E; e is 0, 1, 2, 3, 4 or 5; f is 0, 1, 2 or 3; g is 0, 1, 2, 3 or 4; h is 0, 1 or 2; or two adjacent groups R.sup.26, R.sup.27 R.sup.28 or R.sup.29 may form together with the atoms to which they are bonded a ring structure which may be substituted by G, wherein is a bonding site.

10: An organic electronic device, comprising the compound according to claim 1.

11: The organic electronic device according to claim 10, which is an organic electroluminescent device, wherein the organic electroluminescent device comprises an organic thin film layer between a cathode and an anode, wherein the organic thin film layer comprises one or more layers and comprises a light emitting layer, and at least one layer of the organic thin film layer comprises the compound of formula (I).

12: The organic electronic device according to claim 11, wherein the light emitting layer comprises the compound of formula (I).

13: The organic electronic device according to claim 11, wherein the light emitting layer comprises a phosphorescent material, which is an ortho-metallated complex comprising a metal atom selected from the group consisting of iridium (Ir), osmium (Os) and platinum (Pt).

14: A charge transport layer, charge/exciton blocking layer, or an emitting layer comprising the compound according to claim 1.

15: The emitting layer according to claim 14, comprising the compound of formula (I) as host material in combination with a phosphorescent emitter.

16: An apparatus selected from the group consisting of stationary visual display units; mobile visual display units; illumination units; keyboards; items of clothing; furniture; wallpaper, the apparatus comprising the organic electronic device according to claim 10.

17: A device, comprising the compound of claim 1, wherein the device is selected from the group consisting of organic electroluminescent devices, electrophotographic photoreceptors, photoelectric converters, organic solar cells, switching elements, organic light emitting field effect transistors, image sensors and dye lasers.

18: A process for preparing the compound of claim 1, the process comprising: i) preparing the compound of formula (I), wherein R.sup.6 and R.sup.7 form together a ring system of formula IIa, comprising: ia) preparing an intermediate of formula IIIa; ##STR01676## and ib) cyclizing the intermediate to form the compound of formula (I); ii) preparing the compound of formula (I), wherein R.sup.2 and R.sup.3 form together a ring system of formula IIb, comprising: iia) preparing an intermediate of formula IIIb or IIIb: ##STR01677## and iib) cyclizing the intermediate to form the compound of formula (I); iii) preparing the compound of formula (I), wherein R.sup.2 and R.sup.3 form together a ring system of formula IIc, comprising: iiia) preparing an intermediate of formula IIIc: ##STR01678## and iiib) cyclizing the intermediate to form the compound of formula (IIId): ##STR01679## and iiic) functionalizing the NH group to form the compound of formula (I); iv) preparing the compound of formula (I), wherein R.sup.2 and R.sup.3 form together a ring system of formula IIc, comprising: iva) preparing an intermediate of formula IIIe: ##STR01680## and ivb) cyclizing the intermediate to form the compound of formula (I); v) preparing the compound of formula (I), wherein R.sup.6 and R.sup.7 form together a ring system of formula IIc, comprising: va) preparing an intermediate of formula (IIIf): ##STR01681## and vb) cyclizing the intermediate to form the compound of formula (I); vi) preparing the compound of formula (I), wherein R.sup.6 and R.sup.7 form together a ring system of formula IIc, comprising: via) preparing an intermediate of formula (IIIg): ##STR01682## and vib) cyclizing the intermediate to form the compound of formula (I); vii) preparing the compound of formula (I), wherein R.sup.6 and R.sup.7 form together a ring system of formula IIc, comprising: viia) preparing an intermediate of formula (IIIh): ##STR01683## and viib) cyclizing the intermediate to form the compound of formula (I); viii) preparing the compound of formula (I), wherein R.sup.6 and R.sup.7 form together a ring system of formula IIc, comprising: viiia) preparing an intermediate of formula (IIIi): ##STR01684## wherein Hal is halogen; viiib) cyclizing the intermediate to form a compound of formula (IIIj): ##STR01685## and viiic) functionalizing the NH group to form the compound of formula (I); ix) preparing the compound of formula (I), wherein R.sup.2 and R.sup.3 form together a ring system of formula IIc, comprising: ixa) preparing an intermediate of formula (IIIk): ##STR01686## wherein Hal is halogen; ixb) cyclizing the intermediate to form a compound of formula (IIIl): ##STR01687## ixc) functionalizing the NH group to form the compound of formula (I); wherein: R.sup.9 is a group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p-(A.sup.3).sub.q(A.sup.4).sub.r-R.sup.20; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.20 or a group E, or adjacent groups R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, R.sup.6 and R.sup.7, and/or R.sup.7 and R.sup.8 can from together a ring; R.sup.10, R.sup.11, R.sup.12, R.sup.13 are independently of each other H, CN or group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.20 or a group E, or adjacent groups R.sup.10 and R.sup.11, R.sup.11 and R.sup.12 and/or R.sup.12 and R.sup.13 can from together a ring; o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0, or 1; o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0, or 1, A.sup.1, A.sup.2, A.sup.3, A.sup.4 is a C.sub.6-C.sub.24 arylene group which is unsubstituted or substituted by G, C.sub.2-C.sub.24 heteroarylene group which is unsubstituted or substituted by G; R.sup.20 is a C.sub.6-C.sub.24 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted by G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; or, in the case that at last one of o, p, q and r is 1, R.sup.20 is CN; A.sup.1, A.sup.2, A.sup.3, A.sup.4 is a C.sub.6-C.sub.24 arylene group which is unsubstituted or substituted by G, C.sub.2-C.sub.24 heteroarylene group which is unsubstituted or substituted by G; R.sup.20 is H, CN or a C.sub.6-C.sub.24 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted by G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; R.sup.25 is independently of each other C.sub.6-C.sub.18aryl which is unsubstituted or substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.51alkoxy; or C.sub.1-C.sub.18alkyl which is interrupted by O, which is unsubstituted or substituted by E; D is CO, COO, S, SO, SO.sub.2, O, -CR.sup.63CR.sup.64, NR.sup.65, SiR.sup.70R.sup.71, POR.sup.72, or CC; E is OR.sup.69, SR.sup.69, NR.sup.65R.sup.66, COR.sup.68, COOR.sup.67, CONR.sup.65R.sup.66, CN, Si(R.sup.70).sub.3 or halogen; G is E, or a C.sub.1-C.sub.24alkyl group, a C.sub.6-C.sub.24aryl group, a C.sub.6-C.sub.24aryl group, which is substituted by F, C.sub.1-C.sub.24alkyl, C.sub.1-C.sub.24alkyl which is interrupted by O, a C.sub.2-C.sub.30heteroaryl group, or a C.sub.2-C.sub.30heteroaryl group, which is substituted by F, C.sub.1-C.sub.24alkyl, C.sub.1-C.sub.24alkyl which is interrupted by O; R.sup.63 and R.sup.64 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O; R.sup.65 and R.sup.66 are independently of each other a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.51alkyl group, which is interrupted by O, or R.sup.65 and R.sup.66 together form a five or six membered ring, R.sup.67 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.68 is H; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.69 is a C.sub.6-C.sub.18aryl; a C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.70 and R.sup.71 are independently of each other a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; and R.sup.72 is a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl.

19: A compound represented by any one of the following of formulae: ##STR01688## ##STR01689## ##STR01690## wherein: R.sup.9 is a group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p-(A.sup.3).sub.q (A.sup.4).sub.r-R.sup.20; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, which are not forming together a ring system of formula IIa, IIb or IIc are independently of each other H, CN or group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.20 or a group E, or adjacent groups R.sup.1 and R.sup.2, R.sup.2 and R.sup.3, R.sup.3 and R.sup.4, R.sup.5 and R.sup.6, R.sup.6 and R.sup.7, and/or R.sup.7 and R.sup.8 can from together a ring; R.sup.10, R.sup.11, R.sup.12, R.sup.13 are independently of each other H, CN or group of formula -(A.sup.1).sub.o-(A.sup.2).sub.p-(A.sup.3).sub.q-(A.sup.4).sub.r-R.sup.20 or a group E; or CN; adjacent groups R.sup.10 and R.sup.11, R.sup.11 and R.sup.12 and/or R.sup.12 and R.sup.13 can from together a ring; o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0, or 1; o is 0, or 1, p is 0, or 1, q is 0, or 1, r is 0, or 1, A.sup.1, A.sup.2, A.sup.3, A.sup.4 is a C.sub.6-C.sub.24 arylene group which is unsubstituted or substituted by G, C.sub.2-C.sub.24 heteroarylene group which is unsubstituted or substituted by G; R.sup.20 is a C.sub.6-C.sub.24 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted by G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; or, in the case that at last one of o, p, q and r is 1, R.sup.20 is CN; A.sup.1, A.sup.2, A.sup.3, A.sup.4 is a C.sub.6-C.sub.24 arylene group which is unsubstituted or substituted by G, C.sub.6-C.sub.24 heteroarylene group which is unsubstituted or substituted by G; R.sup.20 is H, CN, or a C.sub.6-C.sub.24 aryl group which is unsubstituted or substituted by G, C.sub.2-C.sub.18 heteroaryl group which is unsubstituted or substituted by G, a C.sub.1-C.sub.25alkyl group, which can optionally be substituted by E and or interrupted by D; R.sup.28 is independently of each other C.sub.6-C.sub.18aryl which is unsubstituted or substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; or C.sub.1-C.sub.51alkyl which is interrupted by O, which is unsubstituted or substituted by E; D is CO, COO, S, SO, SO.sub.2, O, -CR.sup.63CR.sup.64, NR.sup.65, SiR.sup.70R.sup.71, POR.sup.72, or CC; E is OR.sup.69, SR.sup.69, NR.sup.65R.sup.66, COR.sup.68, COOR.sup.67, CONR.sup.65R.sup.66, CN, Si(R.sup.70).sub.3 or halogen; G is E, or a C.sub.1-C.sub.24alkyl group, a C.sub.6-C.sub.24aryl group, a C.sub.6-C.sub.24aryl group, which is substituted by F, C.sub.1-C.sub.24alkyl, C.sub.1-C.sub.24alkyl which is interrupted by O, a C.sub.2-C.sub.30heteroaryl group, or a C.sub.2-C.sub.30heteroaryl group, which is substituted by F, C.sub.1-C.sub.24alkyl, C.sub.1-C.sub.24alkyl which is interrupted by O; R.sup.63 and R.sup.64 are independently of each other C.sub.6-C.sub.18aryl; C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; C.sub.1-C.sub.18alkyl; or C.sub.1-C.sub.18alkyl which is interrupted by O; R.sup.65 and R.sup.66 are independently of each other a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O, or R.sup.65 and R.sup.66 together form a five or six membered ring, R.sup.67 is a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl, or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.68 is H; a C.sub.6-C.sub.18aryl group; a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.69 is a C.sub.6-C.sub.18aryl; a C.sub.6-C.sub.18aryl, which is substituted by C.sub.1-C.sub.18alkyl or C.sub.1-C.sub.18alkoxy; a C.sub.1-C.sub.18alkyl group; or a C.sub.1-C.sub.18alkyl group, which is interrupted by O; R.sup.70 and R.sup.71 are independently of each other a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl; and R.sup.72 is a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group, or a C.sub.6-C.sub.18aryl group, which is substituted by C.sub.1-C.sub.18alkyl.

Description

EXAMPLES

[0662] 1,4-difluoro-2,5-dinitrobenzene was synthesized according known literature procedure (US20130237725). 3-phenyl-1H-benzimidazol-2-one was synthesized according known literature procedure (reaction of 1,10-carbonyldiimidazole with N2-phenylbenzene-1,2-diamine; Bioorganic and Medicinal Chemistry Letters, 2008, 18, 6067).

Example 1

[0663] ##STR01612##

[0664] a.) 7.36 g (35.0 mmol) of 3-phenyl-1H-benzimidazol-2-one and 1.40 g (35 mmol) of NaH were mixed together in DMF (110 mL) at 0 C. for 10 min. Then, 3.57 g (17.5 mmol) of 1,4-difluoro-2,5-dinitrobenzene were added by portion. The mixture was stirred 2h at 0 C., precipitated in water and filtrated to yield 9.12 g of 1-1 as a yellow powder [Purity=94% (HPLC)] which was used directly as it is for the next step.

[0665] Mass [M+1]=584.4

##STR01613##

[0666] b.) 8.76 g (15.0 mmol) of 1-1 and 1.00 g of Pd/C 10% were mixed in 125 mL of 5:1 THF:EtOH at 50 C. under 5 bar of dihydrogen for 12h. The mixture was then filtrated, the solvent evaporated and the resulting powder was recrystallized several times from THF to yield 5.58 g of 1-2 [Purity=98.0% (HPLC)] as a yellow powder.

[0667] Mass [M+1]=525.2

##STR01614##

[0668] c.) 5.30 g (10.1 mmol) of 1-2 and 35 g of polyphosphoric acid were mixed together at 240 C. for 6h. The dark brown mixture was then poured into 400 mL of water, filtrated and washed several times with water and MeOH. The product was recrystallized in DMSO then NMP and sublimed 3 times to yield 1.69 g of 1 [Purity=99.79% (HPLC)] as a slightly yellow crystal.

[0669] Mass [M+1]=489.4

Example 2

[0670] ##STR01615##

[0671] a.) 15.72 g (74.8 mmol) of 3-phenyl-1H-benzimidazol-2-one, 6.94 g (34.0 mmol) of 1,3-difluoro-4,6-dinitrobenzene and 28.87 g (136 mmol) of K.sub.3PO.sub.4 were mixed together in NMP (200 mL) at 0 C. for 2h. The mixture was then stirred 2h at room temperature and precipitated in water filtrated to yield 19.44 g of 2-1 as a yellow powder [Purity=85% (H PLC)] which was used directly as it is for the next step.

[0672] Mass [M+1]=584.2

##STR01616##

[0673] b.) 4.38 g (7.5 mmol) of 2-1 and 500 mg of Pd/C 10% were mixed in 60 mL of 3:1 THF:EtOH at 50 C. under 5 bar of dihydrogen for 2h. The mixture was then filtrated, the solvent is evaporated and the resulting powder was purified by chromatography (SiO.sub.2, gradient: toluene/THF) to yield 2.12 g of 2-2 [Purity=99.0% (HPLC)] as a white powder.

[0674] Mass [M+1]=525.3

##STR01617##

c.) 9.11 g (17.4 mmol) of 2-2 and 75 g of polyphosphoric acid were mixed together at 230 C. for 6h. The dark brown mixture was then poured into 650 mL of water, filtrated and washed several times with water and MeOH. The product was recrystallized twice in DMSO, washed with MeOH and sublimed twice. It was again recrystallized in DMSO and sublimed to yield 2.97 g of 2 [Purity 25=99.91% (H PLC)] as a white crystal.

[0675] Mass [M+1]=489.4

[0676] .sup.1H NMR (400 MHz, DMSO): 9.04 (s, 1H), 8.60 (d, 2H), 7.97 (m, 4H), 7.83 (s, 1H), 7.65-7.75 (m, 6H), 7.52 (m, 4H), 7.43 (m, 2H).

Example 3

[0677] ##STR01618##

[0678] a.) 64.38 g (480 mmol) of 1,3-dihydro-2H-benzimidazol-2-one, 29.65 g (120 mmol) of 3-bromodibenzofurane, 27.47 g (120 mmol) of K.sub.3PO.sub.4, 6.85 g (36 mmol) of Cul and 3.41 g (24 mmol) of NN-dimethylcyclohexanediamine were mixed together in dioxane (750 mL) at reflux under inert condition for 16 h. Dioxane was then evaporated and after work-up, the product was dissolved in CHCl.sub.3, mixed with 80 g of SiO.sub.2 and purified by chromatography (SiO.sub.2, gradient:/MeOH) to yield 17.45 g of 3-dibenzofuran-2-yl-1H-benzimidazol-2-one, 3-1 [Purity=99.8% (HPLC)] as a white powder.

[0679] Mass [M+1]=301.3

[0680] .sup.1H NMR (400 MHz, DMSO): 11.2 (s, 1H), 8.34 (d, 1H), 8.22 (dd, 1H), 7.88 (d, 1H), 7.76 (d, 1H), 7.64 (dd, 1H), 7.58 (m, 1H), 7.44 (m, 1H), 7.11 (m, 2H), 7.00 (m, 2H).

##STR01619##

[0681] b.) 5.04 g (16.8 mmol) of 3-dibenzofuran-2-yl-1H-benzimidazol-2-one, 3-1, 1.63 g (8.0 mmol) of 1,3-difluoro-4,6-dinitrobenzene and 6.79 g (32 mmol) of K.sub.3PO.sub.4 were mixed together in NMP (80 mL) at 0 C. for 2h. The mixture was then stirred 2h at room temperature and precipitated in water filtrated to yield 6.43 g of 3-2 as yellow powder [Purity=90% (HPLC)] which was used directly as it is for the next step.

[0682] Mass [M+1]=765.2

##STR01620##

[0683] c.) 6.18 g (8.0 mmol) of 3-2 and 600 mg of Pd/C 10% were mixed in 200 mL of 3:1 THF:EtOH at 50 C. under 5 bar of hydrogen for 2h. The mixture was then filtrated, the solvent is evaporated and the resulting powder was purified by chromatography (SiO.sub.2, gradient: toluene/THF) to yield 5.39 g of 3-3 [Purity=99.1% (HPLC)] as a white powder.

[0684] Mass [M+1]=705.3

##STR01621##

[0685] d.) 3.87 g (5.5 mmol) of 3-3 and 1.77 g (9.4 mmol) of p-toluensulfonic acid were mixed together in 40 mL of methylnaphthalene at 230 C. for 12h. The dark brown mixture was cooled at 100 C., mixed with 40 g of SiO.sub.2 and purified by chromatography (SiO.sub.2, gradient: CHCl3/MeOH), recrystallized twice in acetic acid and sublimed to yield 1.47 g of 3 [Purity=99.97% (HPLC)] as a white crystal.

[0686] Mass [M+1]=669.2

[0687] .sup.1H NMR (400 MHz, TFA): 8 9.29 (s, 1H), 8.72 (d, 2H), 8.59 (d, 2H), 8.44 (s, 1H), 8.25 (d, 2H), 8.19 (d, 2H), 8.13 (m, 2H), 8.04 (m, 4H), 7.95 (m, 4H), 7.85 (m, 2H), 7.69 (m, 2H).

Example 4

[0688] ##STR01622##

[0689] a.) 33.31 g (248 mmol) of 1,3-dihydro-2H-benzimidazol-2-one, 20.00 g (62.1 mmol) of 3-bromo-9-phenylcarbazol, 26.35 g (124.2 mmol) of K.sub.3PO.sub.4, 5.91 g (31.0 mmol) of Cul and 4.42 g (31.0 mmol) of NN-dimethylcyclohexanediamine were mixed together in N,N-dimethylacetamide (350 mL) at 185 C. under inert condition for 24 h. After work-up, the product was dissolved in CHCl.sub.3, mixed with 70 g of SiO.sub.2 and purified by chromatography (SiO.sub.2, gradient: CHCl.sub.3/MeOH) to yield 15.52 g of 3-(9-phenylcarbazol-3-yl)-1H-benzimidazol-2-one, 4-1 [Purity=98% (HPLC)] as beige crystal.

[0690] Mass [M+1]=376.5

[0691] .sup.1H NMR (400 MHz, DMSO): 11.13 (s, 1H), 8.42 (m, 1H), 8.33 (m, 1H), 7.72 (m, 4H), 7.59 (m, 1H), 7.45-7.56 (m, 3H), 7.42 (m, 1H), 7.33 (m, 1H), 7.10 (m, 2H), 7.02 (m, 1H), 6.97 (m, 1H),

##STR01623##

[0692] b.) 5.00 g (13.3 mmol) of 3-(9-phenylcarbazol-3-yl)-1H-benzimidazol-2-one, 4-1, 1.40 g (6.7 mmol) of 1,3-difluoro-4,6-dinitrobenzene and 5.65 g (26.6 mmol) of K.sub.3PO.sub.4 were mixed together in NMP (80 mL) at 0 C. for 2h. The mixture was then stirred 2h at room temperature and precipitated in water filtrated to yield 9.09 g of 4-2 as yellow powder [Purity=92% (HPLC)] which was used directly as it is for the next step.

[0693] Mass [M+1]=914.3

##STR01624##

[0694] c.) 5.52 g (6.0 mmol) of 4-2 and 550 mg of Pd/C 10% were mixed in 70 mL of 3:1 THF:EtOH at 50 C. under 5 bar of hydrogen for 2h. The mixture was then filtrated, the solvent was evaporated and the resulting powder was purified by chromatography (SiO.sub.2, gradient: toluene/THF) to yield 4.6 g of 4-3 [Purity=99.0% (HPLC)] as a white powder.

[0695] Mass [M+11=854.3

##STR01625##

[0696] d.) 3.63 g (3.6 mmol) of 4-3 and 1.17 g (2.1 mmol) of p-toluensulfonic acid were mixed together in 30 mL of methylnaphthalene at 230 C. for 12h. The dark brown mixture was cooled at 60 C. and mixed with 30 g of SiO.sub.2. It was purified by chromatography (SiO.sub.2, gradient: CHCI3/MeOH), recrystallized twice in acetic acid and sublimed to yield 0.84 g of 4 [Purity=99.81% (H PLC)] as a white crystal.

[0697] Mass [M+1]=818.2

[0698] .sup.1H NMR (400 MHz, CDCl.sub.3): 8.54 (d, 2H), 8.31 (s, 1H), 8.19 (m, 3H), 8.06 (d, 2H), 7.85 (dd, 2H), 7.60-7.72 (m, 10H), 7.44-58 (m, 10H), 7.31-7.42 (m, 4H).

Example 5

[0699] ##STR01626##

[0700] a.)N-(2-nitrophenyl)-2-phenyl-aniline, 5-1, was prepared according to Synthesis 1980, 3, 215. 7.06 g (50.0 mmol) 1-fluoro-2-nitro-benzene and 9.31 g (55 mmol) 2-phenylaniline were stirred under nitrogen. 11.6 g (200 mmol) potassium fluoride was added. The reaction mixture was stirred at 220 C. under nitrogen for 24 h.

[0701] The reaction mixture was poured in water and was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. The solvent was removed in vacuum.

[0702] Column chromatography on silica gel with hexane/toluene 15/85 gave the red product. Yield 10.3 g (71%)

[0703] .sup.1H NMR (400 MHz, CDCl3): 9.35 (s, 1H), 8.14 (dd, 1H), 7.32-7.48 (m, 10H), 7.18 (dd, 1H), 6.74 (td, 1H),

##STR01627##

[0704] b.) To 10.2 g (35.0 mmol)N-(2-nitrophenyl)-2-phenyl-aniline, 5-1, in 120 ml toluene 950 mg Pd on carbon (5%) was added. The reaction mixture was stirred under 5 bar hydrogen for 3 h. The catalyst was filtered of and the solvent was removed in vacuum. Yield of 5-2: quantitative

[0705] .sup.1H NMR (400 MHz, CDCl3): 7.48-7.58 (m, 4H), 7.41 (tt, 1H), 7.19-7.29 (m, 2H), 7.12 (dd, 1H), 7.06 (td, 1H), 6.93 (td, 1H), 6.74-6.83 (m, 3H), 5.34 (s, 1H), 3.78 (s, 2H).

##STR01628##

[0706] c.) 833 mg (3.20 mmol) N2-(2-phenylphenyl)benzene-1,2-diamine, 5-2, and 623 mg (3.84 mmol) di(imidazol-1-yl)methanone in 8 ml THF were stirred at 25 C. under nitrogen for 3 h.

[0707] The reaction mixture was poured in water and was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. The solvent was removed in vacuum.

[0708] Column chromatography on silica gel with toluene/ethyl acetate 2/1 gave the product, 5-3. Yield 10.3 g (71%)

[0709] .sup.1H NMR (400 MHz, CDCl3): 9.81 (s, 1H), 7.50-7.61 (m, 4H), 7.27-7.31 (m, 2H), 7.13-7.23 (m, 3H), 6.97-7.03 (m, 2H), 6.89-6.94 (m 1H), 6.63 (d, 1H).

[0710] d.) 1-[2,4-dinitro-5-[2-oxo-3-(2-phenylphenyl)benzimidazol-1-yl]phenyl]-3-(2-phenylphenyl)benzimidazol-2-one, 5-4, was prepared according to example 1a

##STR01629##

[0711] e.) 1-[2,4-diamino-5-[2-oxo-3-(2-phenylphenyl)benzimidazol-1-yl]phenyl]-3-(2-phenylphenyl)benzimidazol-2-one, 5-5, was prepared according to example 1b

##STR01630##

[0712] f.) 5 was prepared according to example 1 c

##STR01631##

Example 6

[0713] ##STR01632##

a.) 1.10 g (5.00 mmol) 4-bromo-2-fluoro-1-nitro-benzene and 931 mg (5.50 mmol) 2-phenylaniline were stirred under nitrogen. 1.16 g (20.0 mmol) potassium fluoride was added. The reaction mixture was stirred at 220 C. under nitrogen for 24 h.

[0714] The reaction mixture was poured in water and was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. The solvent was removed in vacuum.

[0715] Column chromatography on silica gel with hexane/toluene 15/85 gave the red product, 6-1.

[0716] .sup.1H NMR (400 MHz, CDCl3): 9.41 (s, 1H), 7.98 (d, 1H), 7.28-7.51 (m, 9H), 7.24 (d, 1H), 8.81 (dd, 1H).

Example 7

Example 7a

[0717] ##STR01633##

[0718] To 30.5 g (0.200 mol) 2-chlorobenzimidazole and 28.1 g (0.220 mol) 2-chloroaniline in 50 ml NMP 19.22 g (0.200 mmol) methane sulphonic acid was added. The reaction mixture was stirred at 100 C. for 18 h under nitrogen. The reaction mixture was poured on a saturated solution of sodium hydrogen carbonate in water. The water phase was extracted with ethyl acetate. The organic phase was 3 times washed with water and the organic phase was dried with magnesium sulfate. The solvent was removed in vacuum. The product was decocted in 100 ml dichloromethane.

[0719] Yield 44.8 g (92%)

[0720] .sup.1H NMR (400 MHz, DMSO-d6): =11.0 (s, 1H), 9.66 (s, 1H), 8.09 (t, 1H). 7.56-7.59 (m, 1H), 7.30-7.40 (m, 3H), 6.95-7.05 (m, 3H)

Example 7b

[0721] ##STR01634##

[0722] 25.4 g (0.100 mol) 1,4-dibromo-2-fluorobezene, 24.4 g (0.100 mol)N-(3-chlorophenyl)-1H-benzimidazol-2-amine and 63.7 g (0.300 mol) potassium phosphate tribasic in 130 ml DMA were stirred at 160 C. for 3 h under nitrogen. The reaction mixture was cooled to 25 C. The Product was filtered off and was washed with water. The product was decocted in ethanol.

[0723] Yield 34.5 g (87%).

[0724] .sup.1H NMR (400 MHz, CDCl3): =7.99 (d, 1H), 7.77-7.86 (m, 4H), 7.59 (t, 1H), 7.34-7.51 (m, 5H).

Example 7c

[0725] ##STR01635##

[0726] 19.8 g (50 mmol) 2-bromo-5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazole, 9.00 g (50 mmol) (2-methoxycarbonylphenyl)boronic acid and 53.1 g (0.250 mol) potassium phosphate tribasic in 200 ml DMF were degassed with argon. 2.46 g (6.00 mmol) 2-Dicyclohexylphosphino-2,6-di-methoxybiphenyl (sPhos) and 224 mg (1.00 mmol) palladium (11) acetate were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 19 h at 100 C. under argon.

[0727] The reaction mixture was poured on water and the product was filtered off. The product was decocted with 200 ml ethanol.

[0728] Yield 15.5 g.

[0729] .sup.1H NMR (400 MHz, CDCl3): =7.81-7.97 (m, 6H), 7.58-7.66 (m, 3H), 7.50-7.54 (m, 2H), 7.45-7.48 (m, 1H), 7.38-7.42 (m, 1H), 7.30-7.34 (m, 2H), 3.73 (s, 3H)

Example 7d

[0730] ##STR01636##

[0731] To 0.904 g (2.00 mmol) methyl 2-[5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazol-2-yl]benzoate in 20 ml waterfree THF, 3.13 ml (5.00 mmol) of a 1.6 M solution of methyl lithium in ether was added under argon at 78 C. The reaction mixture was warmed to 0 C. and was stirred at 0 C. for 3 h. The reaction mixture was poured on ice. A 10% solution of tartaric acid was added and the reaction mixture was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. Column chromatography with toluene/ethyl acetate 10/1 gave the product.

[0732] In an alternative process, compound 7-4 was prepared as follows:

[0733] To 14.9 g (33.0 mmol) methyl 2-[5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazol-2-yl]benzoate in 160 ml waterfree THF, 55 ml (0.165 mol) of a 3 M solution of methyl magnesium-chloride in THF was added under argon at 0 C. The reaction mixture was stirred at 50 C. for 3 h. The reaction mixture was poured on ice. A 10% solution of tartaric acid was added and the reaction mixture was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. Column chromatography with toluene/ethyl acetate 10/1 gave the product.

[0734] .sup.1H NMR (400 MHz, CDCl3): =7.94 (t, 1H), 7.86-7.89 (m, 1H), 7.72-7.82 (m, 4H), 7.60 (t, 2H), 7.20-7.48 (m, 8h), 1.57 (s, 6H).

Example 7e

[0735] ##STR01637##

[0736] To 30.0 g PPA (polyphosphoric acid) and 22.5 g methane sulfonic acid 4.30 g (9.53 mmol) 2-[2-[5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazol-2-yl]phenyl]propan-2-ol in in 60 ml dichloromethane was added at 0 C. The reaction mixture was stirred at 25 C. for 2 h.

[0737] The reaction mixture was poured on ice, neutralized with sodium hydrogen carbonate. The water phase was extracted with dichloromethane. The organic phase was dried with magnesium sulfate.

[0738] .sup.1H NMR (400 MHz, CDCl3): =8.11 (s, 1H), 7.98-7.80 (m, 5H), 7.62 (t, 1H), 7.54 (s, 1H), 7.35-7.51 (m, 6h), 1.58 (s, 6H).

Example 7f

[0739] ##STR01638##

[0740] 0.77 mg (1.77 mmol) of the product of example 7e, 470 mg (1.86 mmol) 4,4,5,5-tetramethyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,3,2-, dioxaborolane and 520 mg (5.30 mmol) potassium acetate in 20 ml waterfree toluene were degassed with argon. 254 mg (0.532 mmol) 2-dicyclohexylphosphino-2,4,6-triisoproxylbiphenyl (xPhos) and 81 mg (0.089 mmol) tris (dibenzylidene-acetone) palladium(0) (Pd.sub.2(dba).sub.3) was added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 25 h at 130 C. under argon. 1 ml water and 100 mg sodium cyanide were added. The reaction mixture was stirred at 100 C. for 1 h. The reaction mixture was poured on water and was extracted with diethyl ether. The organic phase was dried with magnesium sulfate. The product was used without purification for the next reaction.

Example 7g

[0741] ##STR01639##

[0742] 930 mg (1.77 mmol) of the product of example 7f, 570 mg (2.12 mmol) 2-chloro-4,6-diphenyl-1,3,5-triazine and 490 mg (3.54 mmol) potassium carbonate in a mixture of 15 ml THF, 15 ml toluene and 5 ml water were degassed with argon. 102 mg (0.089 mmol) tetrakis(triphenylphosphine)palladium(0) (Pd(Ph.sub.3).sub.4) were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 11 h at 90 C. under argon. 10 ml of a 1% solution of sodium cyanide in water was added and the reaction mixture was stirred at 100 C. for 1 h. The product was poured on ethanol and the product was filtered off.

[0743] Column chromatography on silica gel with toluene/ethyl acetate 20/1 gave the product.

[0744] .sup.1H NMR (400 MHz, CDCl3): =8.29-8.30 (m, 1H), 8.91-8.94 (m, 1H), 8.81-8.84 (m, 4H), 8.33-8.36 (m, 1H), 8.20 (s, 1H), 8.02-8.04 (m, 1H), 7.82-7.85 (m, 4H), 7.36-7.66 (m, 11H), 1.61 (s, 6H).

Example 8

Example 8a

[0745] ##STR01640##

[0746] 3.97 mg (10 mmol) 2-bromo-5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazole (compound 7-2, example 7b), 1.64 g mg (10 mmol) (2-acetylphenyl)boronic acid and 2.76 g (20.0 mmol) potassium carbonate in a mixture of 30 THF, 30 ml toluene and 10 ml water were degassed with argon. 580 mg (0.50 mmol) tetrakis(triphenylphosphine)palladium(0) (Pd(Ph.sub.3).sub.4) were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 6 h at 100 C. under argon.

[0747] The reaction mixture was poured on water and the organic phase was extracted with ethyl acetate. The organic phase was dried with magnesium sulfate. The solvent was removed in vacuum. The product was decocted with ethanol.

[0748] .sup.1H NMR (400 MHz, CDCl3): =7.93-7.92 (m, 1H), 7.81-7.87 (m, 4H), 7.31-7.68 (10H), 2.18 (s, 3H).

Example 8b

[0749] ##STR01641##

[0750] To 1.09 g (2.50 mmol) 1-[2-[5-(3-chlorophenyl)benzimidazolo[1,2-a]benzimidazol-2-yl]phenyl]ethanone in 50 ml waterfree THF 4.2 ml (12.5 mmol) of a 3 M solution of methyl magnesium chloride in THF was added under argon at 0 C. The reaction mixture was stirred under argon for 1 h.

[0751] The reaction mixture was poured on ice. ammonium chloride was added and the reaction mixture was extracted with ethyl acetate. The organic phase was dried with magnesium sulfate.

[0752] Column chromatography with toluene/ethyl acetate 10/1 gave the product.

Example 8c

[0753] ##STR01642##

[0754] Compound 7-5 was prepared as described in example 7e.

Example 8d

[0755] ##STR01643##

[0756] 1.00 g (2.30 mmol) of the product 7-5 of example 7e, 733 mg (3.46 mmol) dibenzofuran-2-ylboronic acid and 1.96 g (9.22 mmol) potassium phosphate tribasic in 20 ml dioxane, 50 ml toluene and 20 ml water were degassed with argon. 57 mg (0.84 mmol) 2-Dicyclohexylphosphino-2,6-di-methoxybiphenyl (sPhos) and 5.2 mg (0.14 mmol) palladium (II) acetate were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 4 h at 90 C. under argon.

[0757] 40 ml of a 1% solution of sodium cyanide in water was added and the reaction mixture was stirred at 100 C. for 1 h. The water phase was extracted with toluene and the organic phase was dried with magnesium sulfate. The product was removed in vacuum. Column chromatography on siliga gel with dichloromethane/heptane 1/1 and then dichloromethane gave the product.

[0758] .sup.1H NMR (400 MHz, CDCl3): =8.28 (d, 1H), 8.19-9.20 (m, 1H), 8.16 (s, 1H), 7.99-8.03 (m, 2H), 7.86-7.90 (m, 2H), 7.79-7.85 (m, 4H), 7.70 (d, 1H), 7.61-7.64 (m, 2H), 7.36-7.53 (m, 7H), 1.58 (s, 6H).

Example 9

[0759] ##STR01644##

[0760] The product was prepared as described in example 8d, whereby dibenzofuran-2-ylboronic acid was replaced by

##STR01645##

[0761] .sup.1H NMR (400 MHz, CDCl.sub.3): =9.08-9-09 (m, 1H), 8.80-8.86 (m, 5H), 8.23-8.24 (m, 1H), 8.16 (s, 1H), 7.81-8.02 (m, 7H), 7.73 (t, 1H), 7.57-7.66 (m, 7H), 7.35-7.48 (m, 5H), 1.54 (s, 6H).

Example 10

Example 10a

[0762] ##STR01646##

[0763] To 38.1 g (0.250 mol) 2-chlorobenzimidazole, 25.6 g 0.275 mol) aniline in 250 ml NMP 26.4 g (0.275 mmol) methane sulphonic acid were added. The reaction mixture was stirred at 100 C. for 3 h under nitrogen. The reaction mixture was poured on a saturated solution of sodium hydrogen carbonate in water. The water phase was extracted with ethyl acetate. The organic phase was 3 times washed with water and the organic phase was dried with magnesium sulfate. The solvent was removed in vacuum. The product was decocted in 100 ml dichloromethane.

[0764] Yield 43.6 g (83%)

[0765] .sup.1H NMR (400 MHz, DMSO-d6): =10.9 (s, 1H), 9.38 (s, 1H), 7.29-7.36 (d, 2H), 2.29-7.36 (m, 4H), 6.96-7.02 (m, 2H), 6.91-6.94 (m, 1H).

Example 10b

[0766] ##STR01647##

[0767] 28.5 g (0.112 mol) 1,3-dibromo-4-fluorobezene, 23.5 g (0.112 mol)N-phenyl-1H-benzimidazol-2-amine and 59.6 g (0.281 mol) potassium phosphate tribasic in 250 ml DMA were stirred at 160 C. for 20 h under nitrogen. The reaction mixture was poured on water. The product was filtered off washed with water and ethanol.

[0768] Yield 38.9 g (97.6%).

[0769] .sup.1H NMR (400 MHz, CDCl3): =7.78-7.83 (m, 4H), 7.64-7.70 (m, 4H), 7.48-7.52 (m, 2H), 7.40 (dt, 1H), 7.33 (dt, 1H).

Example 10c

[0770] ##STR01648##

[0771] 10.9 g (30.0 mmol) of 3-bromo-5-phenyl-benzimidazolo[1,2-a]benzimidazole, 5.74 g (45.0 mmol) 2-chloroaniline and 5.77 g (60.0 mmol) potassium t-butoxide in 90 ml toluene were degassed with argon. 550 mg (0.600 mmol) Tris(dibenzylideneacetone)dipalladium(0) and 520 mg (0.900 mmol) 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (Xanphos) were added. The reaction mixture was degassed with argon. The reaction mixture was stirred for 3 h at 90 C. under argon.

[0772] The reaction mixture was poured on water and the organic phase was extracted with dichloromethane. The organic phase was dried with magnesium sulfate. The product was filtered on silica gel and was decocted with ethanol.

[0773] .sup.1H NMR (400 MHz, CDCl3): =7.76, 7.85 (m, 5H), 7.63 (t, 1H), 7.46 (t, 1H), 7.29-7.40 (m, 4H), 7.1-7.23 (m, 3H), 6.81-6.85 (m, 1H), 6.21 (s, 1H)

Example 10d

[0774] ##STR01649##

[0775] 11.1 g (27.1 mmol)N-(2-chlorophenyl)-5-phenyl-benzimidazolo[1,2-a]benzimidazol-3-amine and 11.3 g (81.4 mmol) potassium carbonate in 80 ml waterfree DMA were degassed with argon. 305 mg (1.36 mmol) palladium (II) acetate and 1.00 g (2.72 mmol) tricyclohexylphosphine tetra-fluoroborate was added. The reaction mixture was degassed with argon. The reaction was stirred at 100 C. for 19 h.

[0776] 100 ml 0.5% sodium cyanide solution was added and the reaction mixture was refluxed for 2 h. The product was filtered off and washed with water and ethanol. Column chromatography on silica gel with dichloromethane/ethyl acetate 95/5 gave the product. 5.70 g (56%)

[0777] .sup.1H NMR (400 MHz, CDCl.sub.3): =8.41 (s, 1H), 8.32 (s, 1H), 8.21 (d, 1H), 7.98-8.02 (m, 1H), 7.89-7.92 (m, 2H), 7.80-7.84 (m, 1H), 7.62, 7.67 (m, 2H), 7.52 (s, 1H), 7.44-7.49 (m, 3H), 7.32-7.42 (m, 3H).

Example 10e

[0778] ##STR01650##

[0779] To 3.00 g (8.06 mmol) of the product 10-4 of example 10d in 60 ml waterfree THF 3.87 ml (9.67 mmol)N-butyl lithium 2.5 M in hexane were added at 78 C. under argon. The reaction was stirred at 78 C. for 1 h and 2.37 g (8.86 mmol) 2-chloro-4,6-diphenyl-1,3,5-triazine in 20 ml waterfree THF were added. The reaction mixture was stirred at 78 C. for 2 h and was then refluxed for 26 h.

[0780] The product was filtered off and was washed with ethanol, water and again with ethanol. The product was decocted in ethanol. Yield 1.18 g (24%)

[0781] .sup.1H NMR (400 MHz, TFA-d1): =9.68 (s, 1H), 9.35 (d, 1H), 8.97 (s, 1H), 8.60 (sb, 2H), 8.43-8.47 (m, 2H), 8.22 (sb, 2H), 7.62-7.82 (m, 16H).

Example 11

[0782] ##STR01651##

[0783] To 2.59 g (6.71 mmol) of the product 10-4 of example 10d, 2.48 g (6.38 mmol) 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine 4.27 g (20.1 mmol) potassium phosphate and 510 mg (2.69 mmol) copper(I)iodide were added in 100 ml dioxane. It was stirred under nitrogen at 100 C. 7.67 g (67.3 mmol) cis,trans diaminocyclohexane was added, and the reaction mixture was stirred for 15 h. The reaction temperature was increased to 120 C., and the reaction mixture was stirred for 3.5 days.

[0784] The reaction mixture was poured on methanol and the product was filtered off. The product was washed with ethanol, water and again with ethanol. Yield 3.15 g (69%).

[0785] .sup.1H NMR (400 MHz, CDCl.sub.3): =9.05 (s, 1H), 8.88-8.93 (m, 1H), 7.78 (d, 4H), 8.53 (s, 1H), 8.32 (d, 1H), 8.04-8.09 (m, 1H), 7.81-7.86 (m, 5H), 7.39-7.65 (m, 14H), 7.32-7.30 (m, (under CDCl.sub.3)).

[0786] .sup.1H NMR (400 MHz, THF-d8): =8.18 (t, 1H), 8.98 (dt, 1H), 8.83-8.86 (m, 5H), 8.38-8.41 (m, 1H), 8.19-8.21 (m, 1H), 7.98-8.01 (m, 3H), 7.93 (t, 1H), 7.78 (s, 1H), 7.55-7.70 (m, 8H), 7.31-7.48 (m, 6H), 7.26 (dt, 1H).

Example 12

Example 12a

[0787] ##STR01652##

[0788] Compound 12-3 was prepared in analogy to compound 10-3 (example 1 Oc), whereby 3-bromo-5-phenyl-benzimidazolo[1,2-a]benzimidazole was replaced by 4-bromo-5-phenyl-benzimidazolo[1,2-a]benzimidazole.

[0789] .sup.1H-NMR (400 MHz, CDCl.sub.3): =7.86-7.88 (m, 1H), 7.75-7.78 (m, 1H), 7.66 (dd, 1H), 7.27-7.51 (m, 9H), 7.18 (dd, 1H), 7.06 (dt, 1H), 6.95 (dd, 1H), 6.75 (dt, 1H), 5.66 (sb, 1H).

Example 12b

[0790] ##STR01653##

[0791] Compound 12-4 was prepared in analogy to compound 10-4 (example 10d).

[0792] .sup.1H-NMR (400 MHz, CDCl.sub.3): =8.13-8.17 (m, 2H), 7.97, 7.99 (m, 1H), 7.90-7.93 (m, 2H), 7.81-7.84 (m, 2H), 7.74-7.79 (m, 2H), 7.73 (sb, 1H), 7.60-7.65 (m, 1H), 7.31-7.47 (m, 5H).

APPLICATION EXAMPLES

Application Example 1

[0793] A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode was first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate was exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below were applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 /sec at about 10.sup.6-10.sup.8 mbar. As a hole injection layer, 40 nm-thick of compound A was applied. Then 20 nm-thick of compound B was applied as a hole transporting layer. Subsequently, a mixture of 20% by weight of an emitter compound, (Ir(Ph-ppy).sub.3), 40% by weight of a 1.sup.st host (compound C) and 40% by weight of a 2.sup.nd host (compound 2) were applied to form a 40 nm-thick phosphorescent-emitting layer. On the emitting layer, 30 nm-thick compound D was applied as an electron transport layer. Finally, 1 nm-thick LiF was deposited as an electron injection layer and 80 nm-thick Al was then deposited as a cathode to complete the device. The device was sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen.

##STR01654## ##STR01655##

Application Example 2

[0794] Application Example 1 was repeated except that the host (compound 2) was replaced by compound 1. The device results are shown in Table 1.

##STR01656##

OLED Characterization

[0795] To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristic was measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U, EQE and Commission Internationale de I'clairage (CIE) coordinate are given at 10 mA/cm.sup.2 except otherwise stated.

TABLE-US-00013 TABLE 1 Appl. Ex. 2.sup.nd Host U (V) EQE (%) CIE, x/y Appl. Ex. 1 Compound 2 4.8 15.9 0.33/0.62 Appl. Ex. 2 Compound 1 4.8 15.5 0.34/0.61

[0796] The results shown in Table 1 demonstrate that the compound 2 and 1 can be used as host material in an OLED together with a green emitter.

[0797] Also, compounds 3, 4 and 5 can be used as host material in an OLED with the same structure as mentioned in application example 1 together with a green emitter. Said OLED emits green light.

Comparative Application Example 1

[0798] A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode was first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate was exposed to an ultraviolet light and ozone for further 30 min. This treatment also improves the hole injection properties of the ITO. The cleaned substrate was mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below were applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 /sec at about 10.sup.6-10.sup.8 mbar. As a hole injection layer, 5 nm-thick of compound A was applied. Then 100 nm-thick of compound B and 60 nm-thick compound C were applied as hole transporting layer 1 and hole transporting layer 2, respectively. Subsequently, a mixture of 5% by weight of an emitter compound (Ir(ppy).sub.3), 47.5% by weight of a host (comparative compound 1) and 47.5% by weight of compound E were applied to form a 40 nm-thick phosphorescent-emitting layer. On the emitting layer, 30 nm-thick compound D was applied as an electron transport layer. Finally, 1 nm-thick LiF was deposited as an electron injection layer and 80 nm-thick Al was then deposited as a cathode to complete the device. The device was sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen.

##STR01657## ##STR01658##

OLED Characterization

[0799] To characterize the OLED, electroluminescence spectra were recorded at various currents and voltages. In addition, the current-voltage characteristic was measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U and EQE are given at a current density of 10 mA/cm.sup.2, and 80% lifetime (LT80), the time spent until the initial luminance at 50 mA/cm.sup.2 was reduced to 80%, was recorded. The device results are shown in Table 2.

Comparative Application Example 2

[0800] Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by comparative compound 2. The device results are shown in Table 2.

##STR01659##

Application Example 3

[0801] Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by compound 11. The device results are shown in Table 2.

##STR01660##

Application Example 4

[0802] Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by compound 10. The device results are shown in Table 2.

##STR01661##

TABLE-US-00014 TABLE 2 Appl. Ex. Host U [V] LT80 [hrs] CIE(x, y) Comp. Appl. Ex. 1 Comparative 5.55 57.6 0.32/0.63 Compound 1 Comp. Appl. Ex. 2 Comparative 5.32 40.2 0.32/0.63 Compound 2 Appl. Ex. 3 Compound 11 5.24 72.0 0.31/0.63 Appl. Ex. 4 Compound 10 5.10 86.6 0.31/0.63

[0803] The results shown in Table 2 demonstrate that the lifetime and voltage are improved in the case that inventive compounds 11 and 10 are used as green hosts together with a co-host compound E in an OLED.

Comparative Application Example 3

[0804] Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by comparative compound 3. The device results are shown in Table 3.

##STR01662##

Application Example 5

[0805] Comparative Application Example 1 was repeated except that the host (comparative compound 1) was replaced by compound 3. The device results are shown in Table 3.

##STR01663##

TABLE-US-00015 TABLE 3 Appl. Ex. Hosts U [V] LT80 [hrs] CIE(x, y) Comp. Appl. Ex. 3 Comparative 5.16 135 0.31/0.63 Compound 3 Appl. Ex. 5 Compound 7 4.86 187 0.32/0.63

[0806] The results shown in Table 3 demonstrate that the lifetime and voltage are improved in the case that an inventive compound 3 is used as a green host together with a co-host Compound E in an OLED.