HETERO-CONDENSED PHENYLQUINAZOLINES AND THEIR USE IN ELECTRONIC DEVICES

Abstract

The present invention relates to compounds of the general formula (I) and to a process for their preparation, to an electronic device comprising at least one of these compounds, to an emitting layer, preferably present in an electronic device, comprising at least one compound of general formula (I) and to the use of a compound according to general formula (I) in an electronic device as a host material and/or charge transporting material.

##STR00001##

Claims

1: A compound of general formula (I) ##STR00380## wherein X.sup.1 is CR.sup.1 or N, X.sup.2 is CR.sup.2 or N, X.sup.3 is CR.sup.3 or N, X.sup.4 is CR.sup.4 or N, X.sup.5 is CR.sup.5 or N, X.sup.6 is CR.sup.6 or N, X.sup.7 is CR.sup.7 or N, X.sup.8 is CR.sup.8 or N, X.sup.9 is CR.sup.9 or N, X.sup.10 is CR.sup.10 or N, wherein X.sup.1 and X.sup.3 are not CR.sup.1 and CR.sup.3 at the same time, Y is selected from NR.sup.11, O or S, R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 are independently of each other selected from H, E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, or at least two of R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 or R.sup.10, if present at adjacent carbon atoms, together form at least one C.sub.6-C.sub.18aryl or C.sub.1-C.sub.18heteroaryl ring or ring system, o is independently of each other 0 or 1, p is independently of each other 0 or 1, q is independently of each other 0 or 1 and r is independently of each other 0 or 1, L.sup.1, L.sup.2, L.sup.3 and L.sup.4 are independently of each other selected from a C.sub.6-C.sub.40aryl group which is unsubstituted or substituted by at least one group E, C.sub.1-C.sub.24heteroaryl group which is unsubstituted or substituted by at least one group E, R.sup.14 is independently of each other selected from H, E, a C.sub.6-C.sub.24aryl group which is unsubstituted or substituted by at least one group E, C.sub.1-C.sub.24heteroaryl group which is unsubstituted or substituted by at least one group E, a C.sub.1-C.sub.25alkyl group which unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, D is independently of each other CO, COO, S, SO, SO.sub.2, O, CR.sup.15?CR.sup.16, NR.sup.17, SiR.sup.22R.sup.23, POR.sup.25, C?C, E is independently of each other OR.sup.21, SR.sup.21, NR.sup.17R.sup.18, COR.sup.20, COOR.sup.19, CONR.sup.17R.sup.18, CN, SiR.sup.22R.sup.23R.sup.24, POR.sup.25R.sup.27, halogen, a C.sub.6-C.sub.60aryl group which is unsubstituted or is substituted by at least one F, CF.sub.3, CF.sub.2CF.sub.3, CF.sub.2CF.sub.2CF.sub.3, CF(CF.sub.3).sub.2, (CF.sub.2).sub.3CF.sub.3 or C(CF.sub.3).sub.3, a C.sub.1-C.sub.18 alkyl or a C.sub.1-C.sub.18alkyl group which is interrupted by at least one O, a C.sub.1-C.sub.6heteroaryl group which is unsubstituted or substituted by at least one F, CF.sub.3, CF.sub.2CF.sub.3, CF.sub.2CF.sub.2CF.sub.3, CF(CF.sub.3).sub.2, (CF.sub.2).sub.3CF.sub.3 or C(CF.sub.3).sub.3, R.sup.15 and R.sup.16 are independently of each other H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group which is interrupted by at least one O, R.sup.17 and R.sup.18 are independently of each other H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, or R.sup.17 and R.sup.18 together form a five or six membered aliphatic, aromatic or heteroaromatic ring, R.sup.19 is H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, R.sup.20 is H or a C.sub.1-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, R.sup.21 is independently of each other H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, R.sup.22, R.sup.23 and R.sup.24 are independently of each other H, a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group, and R.sup.25 and R.sup.27 are independently of each other H, a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E.

2: The compound according to claim 1, wherein X.sup.1 and X.sup.3 are N.

3: The compound according to claim 1, wherein X.sup.1 is CR.sup.1 and X.sup.3 is N or X.sup.1 is N and X.sup.3 is CR.sup.3.

4: The compound according to claim 1, wherein X.sup.2 is CR.sup.2, X.sup.4 is CR.sup.4, X.sup.5 is CR.sup.5, X.sup.6 is CR.sup.6, X.sup.7 is CR.sup.7, X.sup.8 is CR.sup.8, X.sup.9 is CR.sup.9 and X.sup.10 is CR.sup.10.

5: The compound according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are independently of each other selected from H, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, wherein L.sup.1, L.sup.2, L.sup.3, L.sup.4 are independently of each other selected from a C.sub.6-C.sub.40aryl group which is unsubstituted or substituted by at least one group E or C.sub.1-C.sub.24heteroaryl group which is unsubstituted or substituted by at least one group E, and R.sup.14 is independently of each other selected from H or a C.sub.1-C.sub.25alkyl group which unsubstituted or substituted by at least one group E and/or interrupted by at least one group D.

6: The compound according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10, if present, are independently of each other selected from H, a C.sub.6-C.sub.40aryl group which is unsubstituted or substituted by at least one group E or a C.sub.1-C.sub.24N-comprising heteroaryl group which is unsubstituted or substituted by at least one group.

7: The compound according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10, if present, are independently of each other selected from H, a N-heteroaryl group according to general formula (XII) ##STR00381## wherein n is an integer of 0 to 8, m is an integer of 0 to 4, M is a C.sub.6-C.sub.40 arylene group which is unsubstituted or substituted by at least one group E, a C.sub.1-C.sub.24heteroarylene group which is unsubstituted or substituted by at least one group E or a C.sub.1-C.sub.25 alkylene group which unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, R.sup.26 is independently of each other selected from E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, or at least two of R.sup.26, if present at adjacent carbon atoms, may form at least one five or six membered, substituted or unsubstituted, saturated, unsaturated, aromatic or heteroaromatic ring or ring system, to which at least one further aromatic and/or heteroaromatic ring or ring system may be fused.

8: The compound according to claim 7, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10, if present, are independently of each other selected from H, a N-heteroaryl group according to general formula (XIII) or (XV) ##STR00382## wherein n is 0 to 4, R.sup.28, R.sup.29, R.sup.30, R.sup.31, R.sup.37 and R.sup.38 are independently of each other selected from H, E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, or at least two of R.sup.28, R.sup.29, R.sup.30, R.sup.31, R.sup.37 or R.sup.38, if present at adjacent carbon atoms, together form at least one C.sub.6-C.sub.18aryl or C.sub.2-C.sub.18heteroaryl ring or ring system, and Q and T are independently of each other selected from direct bond, S, O, SiR.sup.32R.sup.33, CR.sup.34CR.sup.35 or NR.sup.36, wherein R.sup.32 and R.sup.33 are independently of each other H, a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group, R.sup.34 and R.sup.35 are independently of each other H, E, a C.sub.6-C.sub.24aryl group which is unsubstituted or substituted by at least one group E, C.sub.1-C.sub.24heteroaryl group which is unsubstituted or substituted by at least one group E, a C.sub.1-C.sub.25alkyl group which unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, or spiro group, wherein R.sup.34 and R.sup.35 together form a five or six membered, substituted or unsubstituted, aliphatic ring, R.sup.36 is H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, ##STR00383## R.sup.28, R.sup.29, R.sup.30, R.sup.31, R.sup.43 and R.sup.44 are independently of each other selected from H, E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, or at least two of R.sup.28, R.sup.29, R.sup.30 or R.sup.31, if present at adjacent carbon atoms, together form at least one C.sub.6-C.sub.18aryl or C.sub.2-C.sub.18heteroaryl ring or ring system, and Q and T are independently of each other selected from direct bond, S, O, SiR.sup.32R.sup.33, CR.sup.34R.sup.35 or NR.sup.36, wherein R.sup.32 and R.sup.33 are independently of each other H, a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group, R.sup.34 and R.sup.35 are independently of each other H, E, a C.sub.6-C.sub.24aryl group which is unsubstituted or substituted by at least one group E, C.sub.1-C.sub.24heteroaryl group which is unsubstituted or substituted by at least one group E, a C.sub.1-C.sub.25alkyl group which unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, or spiro group, wherein R.sup.34 and R.sup.35 together form a five or six membered, substituted or unsubstituted, aliphatic ring, R.sup.36 is H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, wherein D and E have the same meanings as mentioned above.

9: The compound according to claim 7, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10, if present, are independently of each other selected from H, a N-heteroaryl group according to general formula (XIV) ##STR00384## wherein R.sup.39, R.sup.40, R.sup.41, R.sup.42 are independently of each other selected from H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O,

10: The compound according to claim 7, wherein m is 1, M is a C.sub.6-C.sub.40arylene group which is unsubstituted or substituted by at least one group E,

11: The compound according to claim 7, wherein R.sup.1, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10 are H and R.sup.2 is a N-heteroaryl group according to general formula (XII).

12: The compound according to claim 1, wherein R.sup.11 is phenyl.

13: The compound according to claim 7, wherein R.sup.26 represents a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, n is 1 and one of L.sup.1, L.sup.2, L.sup.3, L.sup.4 represents carbazole group and R.sup.14 represents aromatic or heteroaromatic ring or ring system.

14: The compound according to claim 1, wherein at least one of R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10 and R.sup.11 represent a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, and at least one selected from L.sup.1, L.sup.2, L.sup.3, L.sup.4, R.sup.14 represent heterocyclic group having C.sub.1-C.sub.24 carbon atoms.

15: The compound according to claim 1, wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9 and R.sup.10, if present, are independently of each other selected from H, a heterocyclic group represented by general formula (XXI) ##STR00385## wherein A.sup.1 is CR.sup.62 or N, A.sup.2 is CR.sup.63 or N, A.sup.3 is CR.sup.64 or N, A.sup.4 is CR.sup.65 or N, B.sup.1 is CR.sup.66 or N, B.sup.2 is CR.sup.67 or N, B.sup.3 is CR.sup.68 or N, B.sup.4 is CR.sup.69 or N, Y.sup.1 is independently of each other NR.sup.70; CR.sup.71R.sup.72, O or S R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66, R.sup.67, R.sup.68 and R.sup.69 are independently of each other selected from H, direct bond, E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, and/or at least two of R.sup.2, R.sup.63, R.sup.64 and R.sup.65, if present are directly bonded to the moiety represented by the general formula (XXII) by the two *-locations. ##STR00386## wherein Y.sup.2 is independently of each other NR.sup.73, CR.sup.74R.sup.75, O or S, Z.sup.1 is CR.sup.76, Z.sup.2 is CR.sup.77, Z.sup.1 is CR.sup.78, Z.sup.4 is CR.sup.79, and/or R.sup.62, R.sup.63, R.sup.64 or R.sup.65, if present at adjacent carbon atoms, together form at least one C.sub.6-C.sub.18aryl or C.sub.2-C.sub.18heteroaryl ring or ring system, and/or at least two of R.sup.66, R.sup.67, R.sup.68 and R.sup.69, if present are directly bonded to the moiety represented by the general formula (XXIII) by the two *-locations. ##STR00387## wherein Y.sup.3 is independently of each other NR.sup.80, CR.sup.81R.sup.82, O or S, Z.sup.5 is CR.sup.83; Z.sup.6 is CR.sup.84, Z.sup.7 is CR.sup.85, Z.sup.8 is CR.sup.86, and/or at least two of R.sup.66, R.sup.67, R.sup.68 or R.sup.69, if present at adjacent carbon atoms, together form at least one C.sub.6-C.sub.18aryl or C.sub.1-C.sub.18heteroaryl ring or ring system, R.sup.70, R.sup.73 and R.sup.80 are independently of each other selected from direct bond, H, E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, R.sup.71, R.sup.72, R.sup.74, R.sup.75, R.sup.81 and R.sup.82 are, independently of each other selected from H, direct bond, E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, or R.sup.71 and R.sup.72, R.sup.74 and R.sup.75 and/or R.sup.81 and R.sup.82 together form at least one C.sub.3-C.sub.18-alkyl ring or ring system to which at least one C.sub.1-C.sub.18aryl ring or ring system may be attached, R.sup.76, R.sup.77, R.sup.78, R.sup.79, R.sup.83, R.sup.84, R.sup.85 and R.sup.86 are independently of each other selected from H, direct bond, E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.2saralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, and/or at least two of R.sup.76, R.sup.77, R.sup.78, R.sup.79, R.sup.83, R.sup.84, R.sup.85 or R.sup.86, if present at adjacent carbon atoms, together form at least one C.sub.6-C.sub.18aryl or C.sub.2-C.sub.18heteroaryl ring or ring system, wherein the substituent according to general formula (XXI) is connected to the compound according to general formula (I) via one of R.sup.70, R.sup.73, R.sup.80, R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.66, R.sup.67, R.sup.68, R.sup.69, R.sup.76, R.sup.77, R.sup.78, R.sup.79, R.sup.71, R.sup.72, R.sup.74, R.sup.75, R.sup.81, R.sup.82, R.sup.83, R.sup.84, R.sup.85 or R.sup.86, if present, wherein this respective R.sup.70, R.sup.73, R.sup.80, R.sup.62, R.sup.63, R.sup.64, R.sup.65, R.sup.67, R.sup.68, R.sup.69, R.sup.76, R.sup.77, R.sup.78, R.sup.79, R.sup.71, R.sup.72, R.sup.74, R.sup.75, R.sup.81, R.sup.82, R.sup.83, R.sup.84, R.sup.85 or R.sup.86 is a direct bond, optionally interrupted by a group of formula -(M).sub.m-, in this case, m is an integer of 0 to 4, M is a C.sub.6-C.sub.40 arylene group which is unsubstituted or substituted by at least one group E, a C.sub.1-C.sub.24heteroarylene group which is unsubstituted or substituted by at least one group E or a C.sub.1-C.sub.25 alkylene group which unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, o is independently of each other 0 or 1, p is independently of each other 0 or 1, q is independently of each other 0 or 1 and r is independently of each other 0 or 1, L.sup.1, L.sup.2, L.sup.3 and L.sup.4 are independently of each other selected from a C.sub.6-C.sub.40aryl group which is unsubstituted or substituted by at least one group E, C.sub.1-C.sub.24heteroaryl group which is unsubstituted or substituted by at least one group E, R.sup.14 is independently of each other selected from H, E, a C.sub.6-C.sub.24aryl group which is unsubstituted or substituted by at least one group E, C.sub.1-C.sub.24heteroaryl group which is unsubstituted or substituted by at least one group E, a C.sub.1-C.sub.25alkyl group which unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E, D is independently of each other CO, COO, S, SO, SO.sub.2, O, CR.sup.15?R.sup.16, NR.sup.17, SiR.sup.22R.sup.23, POR.sup.25, C?C, E is independently of each other OR.sup.21, SR.sup.21, NR.sup.17R.sup.18, COR.sup.20, COOR.sup.19, CONR.sup.17R.sup.18, CN, SiR.sup.22R.sup.23R.sup.24, POR.sup.25R.sup.27, halogen, a C.sub.6-C.sub.60aryl group which is unsubstituted or is substituted by at least one F, CF.sub.3, CF.sub.2CF.sub.3, CF.sub.2CF.sub.2CF.sub.3, CF(CF.sub.3).sub.2, (CF.sub.2).sub.3CF.sub.3 or C(CF.sub.3).sub.3, a C.sub.3-C.sub.18 alkyl or a C.sub.1-C.sub.18alkyl group which is interrupted by at least one O, a C.sub.1-C.sub.60heteroaryl group which is unsubstituted or substituted by at least one F, CF.sub.3, CF.sub.2CF.sub.3, CF.sub.2CF.sub.2CF.sub.3, CF(CF.sub.3), (CF.sub.2).sub.3CF.sub.3 or C(CF).sup.3, R.sup.15 and R.sup.16 are independently of each other H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group which is interrupted by at least one O, R.sup.17 and R.sup.18 are independently of each other H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, or R.sup.17 and R.sup.18 together form a five or six membered aliphatic, aromatic or heteroaromatic ring, R.sup.19 is H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, R.sup.20 is H or a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18 alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, R.sup.21 is independently of each other H, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group or at least one C.sub.1-C.sub.18alkoxy group, a C.sub.1-C.sub.18alkyl group or a C.sub.1-C.sub.18alkyl group, which is interrupted by at least one O, R.sup.22, R.sup.23 and R.sup.24 are independently of each other H, a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group, and R.sup.25 and R.sup.27 are independently of each other H, a C.sub.1-C.sub.18alkyl group, a C.sub.6-C.sub.18aryl group which is unsubstituted or substituted by at least one C.sub.1-C.sub.18alkyl group, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12cycloalkyl group which is unsubstituted or substituted by at least one group E.

16: The compound according to claim 15, wherein the heterocyclic group according to general formula (XXI) is represented by any one of general formula (XXIa), (XXIb) or (XXIc) ##STR00388##

17: The compound according to claim 15 wherein one of Y.sup.1, Y.sup.2 and Y.sup.3 is NR.sup.70, NR.sup.73 or NR.sup.80 respectively.

18: The compound according to claim 15, wherein two of Y.sup.1, Y.sup.2 and Y.sup.3 are NR.sup.70, NR.sup.73 or NR.sup.80 respectively.

19: The compound according to claim 15, wherein the substituent according to general formula (XXI) is connected to the compound according to general formula (I) via R.sup.70, R.sup.73 or R.sup.80, if present, wherein this respective R.sup.70, R.sup.73 or R.sup.80 is a direct bond, optionally interrupted by a group of formula -(M)m-, wherein M and m have the meanings as mentioned above.

20: The compound according to claim 7, wherein the N-heteroaryl group according to general formula (XII) corresponds to a group according to general formula (XX) ##STR00389## wherein n is an integer of 0 to 7, v is an integer of 0 to 7, R.sup.60 is independently of each other selected from H, E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, a C.sub.7-C.sub.25aralkyl which is unsubstituted or substituted by at least one group E, a C.sub.5-C.sub.12-cycloalkyl group which is unsubstituted or substituted by at least one group E, is independently R.sup.26 is independently of each other selected from E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D R.sup.61 is independently of each other selected from E, a group of formula -(L.sup.1).sub.o-(L.sup.2).sub.p-(L.sup.3).sub.q-(L.sup.4).sub.r-R.sup.14, a C.sub.1-C.sub.25alkyl group, which is unsubstituted or substituted by at least one group E and/or interrupted by at least one group D, or at least two of R.sup.61, if present at adjacent carbon atoms, may form at least one five or six membered, substituted or unsubstituted, saturated, unsaturated, aromatic or heteroaromatic ring or ring system, to which at least one further aromatic and/or heteroaromatic ring or ring system may be fused.

21: A process for the preparation of a compound according to general formula (I) as defined in claim 1, wherein X.sup.2 is CR.sup.2, at least comprising step (A) (A) coupling of a compound according to general formula (V) ##STR00390## with a compound of formula R.sup.2H to obtain a compound according to general formula (I), wherein A is a selected from Cl, Br, I, F, OSO.sub.2CH.sub.3, and OSO.sub.2CF, or OSO.sub.2C.sub.6H.sub.4CH.sub.3.

22: An electronic device comprising at least one compound as defined in claim 1.

23: The electronic device, according to claim 22, being an organic electroluminescence device comprising a cathode, an anode, and a plurality of organic thin film layers provided between the cathode and the anode, the organic thin film layers comprising an emitting layer comprising the at least one compound of general formula (I).

24: The electronic device according to claim 22, wherein the emitting layer comprises a phosphorescent material, which is an ortho-metallated complex comprising a metal atom selected from iridium (Ir), osmium (Os) and platinum (Pt).

25: An electronic equipment comprising the organic electroluminescence device according to claim 23.

26: An emitting layer comprising at least one compound of general formula (I) as defined in claim 1.

27. (canceled)

28: A material for an organic electroluminescence device comprising at least one compound according to claim 1.

Description

EXAMPLES

Compounds Synthesized

[0962] ##STR00315##

[0963] 2-Amino-6-fluorobenzoic acid (35 g, 225.6 mmol) is dissolved in 885 ml of water and 26 mL of acetic acid. The mixture is stirred at 35? C. for 15 min. After that, sodium cyanate (36.67 g, 564 mmol) dissolved in 442 mL of water is added dropwise to the suspension, and the mixture is stirred at 35? C. for 30 min. Then, sodium hydroxide (180.49 g/4.51 mol) is slowly added to the reaction mixture, the mixture is cooled at room temperature. After 374 mL of hydrogen chloride is added there, the precipitate is collected by filtration and washed with water. The solid is dried in a vacuum oven to yield 37.19 (91.5%) of 1-1 as white solid.

[0964] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 11.25 (s, 1H), 7.65-7.57 (m, 1H), 6.99-6.88 (m, 2H).

[0965] LC-MS (m/z): 179

##STR00316##

[0966] 1-1 (2.6 g, 14.43 mmol) is suspended in 29 mL of toluene and heated to 50? C. Phosphoryl chloride (9.88 mL, 108.25 mmol) is added dropwise, and then DBU (4.31 mL, 28.87 mmol) is added dropwise. The mixture is stirred vigorously at 120? C. for overnight. After the reaction mixture is cooled at room temperature, it is added dropwise to ice-water. The aqueous layer is extracted with ethyl acetate. After it is washed with brine and dried with Na.sub.2SO.sub.4, it is concentrated to give a solid. The crude product is purified by column chromatography on silica gel eluting with toluene to yield 3.41 g (80.8%) of 1-2 as a white powder.

[0967] .sup.1H NMR (300 MHz, CDCl.sub.3) ? 7.99-7.92 (m, 1H), 7.87 (dd, J=8.3, 1.3 Hz, 1H), 7.41 (ddd, J=8.1, 6.5, 1.3 Hz, 1H).

[0968] LC-MS (m/z): 217

##STR00317##

[0969] 1-2 (2.17 g, 10.0 mmol) and 2-hydroxybenzene boronic acid (1.38 g, 10.0 mmol) are dissolved in 10 mL of THF. To the solution is added potassium fluoride (1.74 g, 30.0 mmol) dissolved in 5 mL, and the mixture is evacuated and purged with Argon gas. Then, tBu.sub.3PHBF.sub.4 (290 mg, 1.00 mmol) and Pd(OAc).sub.2 (225 mg, 1.00 mmol) are added to the mixture, and the mixture is stirred at room temperature for 1.5 h. The reaction mixture is dried with MgSO.sub.4, filtrated over Celite and washed with ethyl acetate. The crude is purified by column chromatography on silica gel eluting with a mixed solvent of heptane and ethyl acetate (3:1) to yield 2.27 g (96%) of 1-3 as a slightly yellow solid.

[0970] .sup.1H NMR (300 MHz, CDCl.sub.3) ? 9.98 (s, 1H), 8.00-7.89 (m, 2H), 7.51-7.43 (m, 2H), 7.36 (ddd, J=8.5, 6.8, 1.4 Hz, 1H), 7.15 (dd, J=8.1, 1.1 Hz, 1H), 7.06-7.01 (m 1H).

[0971] LC-MS (m/z): 275

##STR00318##

[0972] 1-3 (3.02 g, 11 mmol) is dissolved in 55 mL of DMF and potassium carbonate (1.67 g, 12.1 mmol) is added. The mixture is stirred at room temperature for 5 min. The reaction mixture is diluted with 100 mL of water, and the solid is collected by filtration and washed with water. It is dried in vacuum oven to yield 2.60 g of 1-4 as a yellow powder.

[0973] .sup.1H NMR (300 MHz, CDCl.sub.3) ? 8.55 (ddd, J=8.5, 6.8, 1.4 Hz, 1H), 7.94 (t, J=8.2H, 1H), 7.74-7.68 (m, 1H), 7.60 (dd, J=8.4, 0.8 Hz, 1H), 7.44-7.40 (m, 2H), 7.32 (dd, J=8.1, 1.0 Hz, 1H)

[0974] LC-MS (m/z): 255

##STR00319##

[0975] 1-4 (1.10 g, 4.32 mmol), 3-(9H-carbazol-3-yl)-9-phenyl-carbazole (1.76 g, 4.32 mmol), and sodium tert-butoxide (581 mg, 6.05 mmol) are added to 43 ml of Toluene. The reaction mixture is evacuated and purged with Argon gas three times. Then, tBu.sub.3PHBF.sub.4 (100 mg, 0.35 mmol) and Pd.sub.2(dba).sub.3 (79 mg, 0.02 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 3 h. The reaction mixture is diluted with water, and the solid is collected by filtration. It is purified by flash chromatography using heptane/toluene=1:1 as an eluent. The isolated product is suspended to toluene and the suspension is stirred at 110? C. overnight. Then the solid is collected by filtration to yield 1.88 g (69%) of Compound 1 as a yellow powder.

[0976] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 9.12-9.05 (m, 2H), 8.78 (d, J=1.8 Hz, 1H), 8.66 (d, J=1.8 Hz, 1H), 8.56 (dd, J=1.8, 8.2 Hz, 1H), 8.43-8.37 (m, 2H), 8.06-8.00 (m, 2H), 7.95 (dd, J=2.0, 8.2 Hz, 1H), 7.87-7.81 (m, 1H), 7.77-7.64 (m, 5H), 7.63-7.42 (m, 8H), 7.38-7.33 (m, 2H)

[0977] LC-MS (m/z): 627

Application Examples

Application Example 1

[0978] A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode is first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate is 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 is mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below are applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 ?/sec at about 10-6-10-8 mbar. As the first layer, 5 nm-thick of electron accepting compound A is vapor-deposited. Then 220 nm-thick of aromatic amine compound B is applied as a hole transporting layer. Then, a mixture of 2% by weight of an emitter compound (Compound D), 98% by weight of a host (compound 1) is applied to form a 40 nm-thick phosphorescent-emitting layer. On the emitting layer, a mixture of 50% by weight of an electron transporting compound, Compound C, 50% by weight of Liq (8-Hydroxyquinolate lithium) is applied to form a 25 nm-thick electron transport layer. Finally, 1 nm-thick Liq is deposited as an electron injection layer and 80 nm-thick Al is then deposited as a cathode to complete the device. The device is sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen.

##STR00320##

Application Example 2

[0979] Application Example 2 is repeated except that the host (compound 1) is replaced by comparative compound (Comparative 1). The device results are shown in Table 1.

##STR00321##

[0980] OLED Characterization

[0981] To characterize the OLED, electroluminescence spectra are recorded at various currents and voltages. In addition, the current-voltage characteristic is measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U, EQE and Commission Internationale de l'Eclairage (CIE) coordinate are given at mA/cm2 except otherwise stated.

TABLE-US-00001 TABLE 1 Appl. Ex. Host U (V) EQE (%) CIE x, y Appl. Ex. 1 Compound 1 5.08 16.7 0.66, 0.34 Appl. Ex. 2 Comparative 1 5.16 16.0 0.66, 0.34

[0982] The results are shown in Table 1. The CIE values show that the electroluminescence is originated from the red emitter compound (Compound D). The compound 1 can show lower driving voltage and higher EQE than the comparative compound (Comparative 1).

Application Example 3

[0983] A glass substrate with 120 nm-thick indium-tin-oxide (ITO) transparent electrode (manufactured by Geomatec Co., Ltd.) used as an anode is first cleaned with isopropanol in an ultrasonic bath for 10 min. To eliminate any possible organic residues, the substrate is 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 is mounted on a substrate holder and loaded into a vacuum chamber. Thereafter, the organic materials specified below are applied by vapor deposition to the ITO substrate at a rate of approx. 0.2-1 ?/sec at about 10-6-10-8 mbar. As a hole injection layer, 50 nm-thick of compound E is applied. Then 45 nm-thick of aromatic amine compound F is applied as a hole transporting layer. Then, a mixture of 3% by weight of an emitter compound G, 97% by weight of a host compound H are applied to form a 20 nm-thick fluorescent-emitting layer. On the emitting layer, 5 nm-thick compound 1 is applied as a first electron transport layer. Then 25 nm-thick compound I is applied as a second electron transport layer. Finally, 1 nm-thick LiF is deposited as an electron injection layer and 80 nm-thick Al is then deposited as a cathode to complete the device. The device is sealed with a glass lid and a getter in an inert nitrogen atmosphere with less than 1 ppm of water and oxygen.

##STR00322##

TABLE-US-00002 TABLE 2 Electron Appl. Ex. transporting layer U (V) EQE (%) CIE x, y Appl. Ex. 3 Compound 1 4.5 6.4 0.14, 0.10

[0984] The results are shown in Table 2. The CIE values show that the electroluminescence is originated from the blue emitter compound G. In addition, application examples 3 show EQEs of more than 6%, which exceeds the theoretical limit of 5%. The results demonstrate that the compound 1 can overcome the pure theoretical limit of 5% by confining triplet excitons in the emitting layer, which enhances triplet-triplet fusion.

Further Synthesis Examples

Compounds Synthesized

[0985] ##STR00323##

[0986] 1-4 (1.21 g, 4.73 mmol), 10-(9H-carbazol-3-yl)-7-phenyl-7H-benzo[c]carbazole (1.67 g, 3.64 mmol), and sodium tert-butoxide (490 mg, 5.10 mmol) are added to 36 mL of Toluene. The mixture reaction is evacuated and purged with argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (85 mg, 0.29 mmol) and Pd.sub.2(dba).sub.3 (67 mg, 0.07 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 5 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The product is recrystallized with dichlorobenzene to yield 1.49 g (41%) of Compound 2 as a yellow powder.

[0987] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 9.15-9.01 (m, 4H), 8.69 (d, J=1.9 Hz, 1H), 8.52 (dd, J=8.3, 1.6 Hz, 1H), 8.42 (dd, J=7.8, 1.4 Hz, 1H), 8.16-8.03 (m, 2H), 7.89 (m, 3H), 7.88-7.70 (m, 6H), 7.69-7.49 (m, 8H), 7.49-7.40 (m, 1H), 7.28 (dd, J=8.1, 0.7 Hz, 1H)

[0988] LC-MS (m/z): 677 [M+1]

##STR00324##

[0989] 1-4 (1.55 g, 6.09 mmol), 14H-benzo[c]benzo[4,5]thieno[2,3-a]carbazole (1.79 g, 5.54 mmol), which is prepared according to the procedure mentioned in US20160028020, and sodium tertbutoxide (745 mg, 7.75 mmol) are added to 55 mL of Toluene. The mixture is evacuated and purged with argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (128 mg, 0.44 mmol) and Pd.sub.2(dba).sub.3 (101 mg, 0.11 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 3.5 h. The reaction mixture is cooled to room temperature. Then, a solid is collected by filtration, and washed with toluene and ethanol. The product is recrystallized with dichlorobenzene to yield 1.97 g (66%) of Compound 3 as a yellow powder.

[0990] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 9.39-9.29 (m, 1H), 9.22 (dd, J=8.3, 1.5 Hz, 1H), 9.06 (d, J=8.4 Hz, 1H), 8.93-8.83 (m, 1H), 8.46-8.35 (m, 2H), 8.19 (t, J=8.2 Hz, 1H), 8.01 (dd, J=8.0, 1.1 Hz, 1H), 8.00-7.79 (m, 3H), 7.77 (dd, J=8.4, 0.8 Hz, 1H), 7.72-7.52 (m, 5H), 7.53-7.43 (m, 2H)

[0991] LC-MS (m/z): 542 [M+1]

##STR00325##

[0992] 1-4 (6.60 g, 25.92 mmol), 4-chlorobenzene boronic acid (6.08 g, 38.87 mmol), and potassium fluoride (4.52 g, 77.7 mmol) are suspended in 260 mL of THF and 5 mL of water. The reaction mixture is evacuated and purged with Argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (752 mg, 2.59 mmol) and Palladium acetate (582 mg, 2.59 mmol) are added to the mixture, and the reaction mixture is stirred at 60? C. for 15 h. The reaction mixture is cooled to room temperature, and a solid is collected by filtration, and washed with ethanol. The product is extracted in Soxhlet extractor with a mixed solvent of THF, chloroform, and ethanol. The solid formed in the solvent is collected by filtration to yield 5.07 g (59%) of 4-1 as a yellow powder.

[0993] LC-MS: 331, 333

##STR00326##

[0994] 4-1 (1.59 g, 4.80 mmol), 14H-benzo[c]benzo[4,5]thieno[2,3-a]carbazole (1.55 g, 4.80 mmol), and sodium tert-butoxide (646 mg, 6.72 mmol) are added to 48 mL of Toluene. The mixture is evacuated and purged with argon gas three times. Then, Di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine (135 mg, 0.38 mmol) and Pd.sub.2(dba).sub.3 (88 mg, 0.10 mmol) are added to the mixture, and the reaction mixture is stirred at 110? C. for 1 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol.

[0995] The product is recrystallized with dichlorobenzene to yield 2.15 g (72%) of Compound 4 as a yellow powder.

[0996] .sup.1H NMR (400 MHz, DMSO-d.sub.6) ? 9.24-9.09 (m, 2H), 9.05-8.92 (m, 3H), 8.87-8.77 (m, 1H), 8.63 (dd, J=7.9, 1.7 Hz, 1H), 8.05-7.95 (m, 4H), 7.91 (ddd, J=8.2, 7.0, 1.1 Hz, 1H), 7.81-7.73 (m, 2H), 7.67-7.58 (m, 2H), 7.57-7.44 (m, 4H), 7.44-7.33 (m, 3H)

[0997] LC-MS (m/z): 618 [M+1]

##STR00327##

[0998] 4-1 (1.67 g, 5.04 mmol), 9H-benzo[a]naphtho[1,2-c]carbazole (1.60 g, 5.04 mmol), which is prepared according to the procedure mentioned in WO2014196580, and sodium tert-butoxide (678 mg, 7.06 mmol) are added to 50 mL of Toluene. The mixture is evacuated and purged with argon gas three times. Then, Di-tert-butyl(2,2-diphenyl-1-methyl-1-cyclopropyl)phosphine (142 mg, 0.40 mmol) and Pd.sub.2(dba).sub.3 (92 mg, 0.10 mmol) are added to the mixture, and the reaction mixture is stirred at 110? C. for 3.5 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The product is recrystallized with dichlorobenzene to yield 2.83 g (92%) of Compound 5 as a yellow powder.

[0999] LC-MS (m/z): 612 [M+1]

##STR00328##

[1000] Benzo[a]carbazole (13.04 g, 60.00 mmol), iodobenzene (18.36 g, 90.00 mmol), and sodium tertbutoxide (8.07 g, 84.00 mmol) are added to 300 mL of toluene. To this mixture are cBRIDP (846 mg, 2.4 mmol) and Pd.sub.2(dba).sub.3 added. Then, the mixture is stirred at 120? C. overnight. After the reaction mixture is cooled at room temperature, it is diluted with toluene. The solid is removed by filtration. The crude product is purified by column chromatography on silica gel eluting with heptane to yield 16.6 g (94%) of 6-1 as a brown resin.

[1001] LC-MS (m/z): 294

##STR00329##

[1002] 6-1 (16.39 g, 55.87 mmol) is dissolved in 100 mL of THF. A suspension of N-bromosuccinimide (9.94 g, 55.87 mmol) in 40 mL of THF is added there, and then the mixture is stirred at room temperature for 1 h. The reaction mixture is diluted with ethanol. Then, the solid is collected by filtration, and washed with ethanol to yield 18.26 g (88%) of 6-2 as an off-white solid. It is used for next reaction without purification.

##STR00330##

[1003] 6-2 (0.93 g, 2.50 mmol), 2-chloroaniline (319 mg, 2.5 mmol), and sodium tert-butoxide (480 mg, 5.00 mmol) are suspended in 25 mL of toluene. Then, .sup.tBu.sub.3PHBF.sub.4 (73 mg, 0.25 mmol) and Pd.sub.2(dba).sub.3 (114 mg, 0.125 mmol) are added to the mixture, and the reaction mixture is stirred at 100? C. for 2.5 h. After the reaction mixture is cooled at room temperature, it is diluted with chloroform, and the solid is removed by filtration. The crude product is purified by column chromatography on silica gel eluting with a mixture of heptane and toluene to yield 497 mg (52%) of 6-3 as a beige solid.

[1004] LC-MS (m/z): 381

##STR00331##

[1005] 1-4 (1.32 g, 5.17 mmol), 6-3 (1.80 g, 4.706 mmol), and sodium tert-butoxide (633 mg, 6.59 mmol) are added to 47 mL of Toluene. The mixture is evacuated and purged with Argon gas three times. Then, 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (120 mg, 0.21 mmol) and Pd.sub.2(dba).sub.3 (86 mg, 0.09 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 1.5 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The product is recrystallized with dichlorobenzene to yield 2.39 g (75%) of Compound 6 as a yellow powder.

[1006] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 9.05-8.96 (m, 2H), 8.34-8.26 (m, 1H), 8.20 (dd, J=8.0, 1.6 Hz, 1H), 8.11 (t, J=8.3, 1H), 7.86-7.75 (m, 4H), 7.74-7.66 (m, 3H), 7.66-7.49 (m, 8H), 7.40 (ddd, J=8.1, 7.2, 1.1 Hz, 1H), 7.28-7.17 (m, 3H)

[1007] LC-MS (m/z): 601 [M+1]

##STR00332##

[1008] 6-2 (5.00 g, 13.43 mmol), nitrobenzene (16.54 g, 134.31 mmol), pivalic acid (412 mg, 4.03 mmol), and potassium carbonate (2.41 g, 17.46 mmol) is suspended in 90 mL of xylene. Then, Pd.sub.2(dba).sub.3 and di-tert-butyl(methyl)phosphonium tetrafluoroborate (0.50 g, 2.02 mmol) are added to the mixture, and the mixture is stirred at 140? C. for 48 h. the solid is removed by filtration, and the filtrate was concentrated. The crude product is purified by column chromatography on silica gel eluting with a mixed solvent of heptane and toluene to yield 2.63 g (47%) of 7-1 as an orange solid.

[1009] LC-MS (m/z): 415

##STR00333##

[1010] 7-1 (2.60 g, 6.27 mmol) and triphenyl phosphine (4.11 g, 15.68 mmol) are suspended in 13 mL of 1,2-dichlorobenzene, and the mixture is stirred at 180? C. overnight. The reaction mixture is cooled at room temperature, and concentrated. The crude product is purified by column chromatography on silica gel eluting with a mixed solvent of heptane and toluene to yield 1.92 g (80%) of 7-2 as a brown solid.

##STR00334##

[1011] 7-2 (1.35 g, 3.53 mmol), 1-4 (0.98 g, 3.88 mmol), and sodium tert-butoxide (475 mg, 4.94 mmol) are added to 35 mL of toluene. The mixture is evacuated and purged with Argon gas three times. Then, 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (90 mg, 0.16 mmol) and Pd.sub.2(dba).sub.3 (65 mg, 0.07 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 3 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene. The crude product is purified by column chromatography on silica gel eluting with a mixed solvent of heptane and toluene (1:2) to yield 2.12 g (75%) of Compound 7 as a yellow powder.

[1012] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 9.11 (d, J=8.4 Hz, 1H), 8.82-8.71 (m, 1H), 8.60-8.50 (m, 1H), 8.16 (dd, J=7.9, 1.6 Hz, 1H), 8.04 (t, J=8.2 Hz, 1H), 7.84-7.73 (m, 5H), 7.70-7.67 (m, 2H), 7.64-7.43 (m, 6H), 7.40-7.31 (m, 2H), 7.13 (ddd, J=8.2, 6.9, 1.2 Hz, 1H), 7.03 (dt, J=8.3, 1.0 Hz, 1H), 6.69 (ddd, J=8.1, 6.9, 1.1 Hz, 1H), 6.58 (dt, J=8.1, 1.0 Hz, 1H)

[1013] LC-MS (m/z): 601 [M+1]

##STR00335##

[1014] 1-4 (1.50 g, 5.87 mmol), 9-phenyl-9H,9H-2,3-bicarbazole (2.00 g, 4.90 mmol), and sodium tert-butoxide (659 mg, 6.85 mmol) are added to 33 mL of Toluene. The mixture is evacuated and purged with Argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (114 mg, 0.39 mmol) and Pd.sub.2(dba).sub.3 (90 mg, 0.10 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 17 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is purified by sublimation twice to yield 3.02 g (98%) of Compound 8 as a yellow powder.

[1015] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 9.46 (d, J=1.5 Hz, 1H), 9.09-9.01 (m, 1H), 8.73 (d, J=1.8 Hz, 1H), 8.61 (dd, J=7.9, 1.6 Hz, 1H), 8.42-8.23 (m, 3H), 8.03 (t, J=8.2 Hz, 1H), 7.93 (dd, J=8.6, 1.8 Hz, 1H), 7.89-7.65 (m, 7H), 7.64-7.40 (m, 8H), 7.37-7.32 (m, 2H)

[1016] LC-MS (m/z): 627 [M+1]

##STR00336##

[1017] 1-4 (1.96 g, 7.70 mmol), 11-phenyl-11,12-dihydroindolo[2,3-a]carbazole (1.79 g, 7.00 mmol) which is prepared according to the procedure mentioned in WO2009116377, and sodium tertbutoxide (942 mg, 9.80 mmol) are added to 50 mL of Toluene. The mixture is evacuated and purged with Argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (162 mg, 0.56 mmol) and Pd.sub.2(dba).sub.3 (128 mg, 0.14 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 17 h.

[1018] The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is column chromatography by eluting with dichloromethane to yield 1.05 g (27%) of Compound 9 as a yellow powder. .sup.1H NMR (400 MHz, DMSO-d.sub.6) ? 8.42-8.31 (m, 4H), 8.27 (d, J=8.1 Hz, 1H), 8.16 (dd, J=7.9, 1.6 Hz, 1H), 7.98 (t, J=8.2 Hz, 1H), 7.81 (ddd, J=8.8, 7.2, 1.7 Hz, 1H), 7.59 (dd, J=8.4 Hz, 1.0 Hz, 1H), 7.53-7.31 (m, 8H), 7.07-6.57 (m, 5H)

[1019] LC-MS (m/z): 550 [M]

##STR00337##

[1020] 1,4-Dibromonaphthalene (5.71 g, 19.97 mmol), 2-nitrobenzene boronic acid (7.00 g, 41.93 mmol) are dissolved in 100 mL of THF. To the solution is a solution of potassium fluoride (6.99 g, 119.81 mmol) dissolved in 10 mL of water added. Then, .sup.tBu.sub.3PHBF.sub.4 (1.16 g, 3.99 mmol) and Pd.sub.2(dba).sub.3 (1.82 g, 2.00 mmol) are there, and the mixture is stirred at room temperature overnight. The solid is removed by filtration, and the filtrate is extracted with ethyl acetate. The solution is partly concentrated to give a beige powder, and it is collected by filtration. And further powder from the filtrate is collected by filtration. Total, 6.77 g (91%) of 10-1 is obtained as a beige powder. It is used for next reaction without further purification.

##STR00338##

[1021] 10-1 (6.72 g, 18.16 mmol) and triphenyl phosphine (28.57 g, 108.95 mmol) are dissolved in 91 mL of 1,2-dichlorobenzene, and the solution is stirred at 180? C. overnight. The solvent is removed by distillation, and the crude product is chromatographed eluting with a mixed solvent of heptane and dichloromethane to yield 4.74 g (85%) of 10-2 as a beige powder. it is used for next reaction without further purification.

##STR00339##

[1022] 10-2 (3.89 g, 12.71 mmol) and iodobenzene (2.59 g, 12.71 mmol) are suspended in 65 mL of toulene. To the suspension are .sup.tBu.sub.3PHBF.sub.4 (295 mg, 1.02 mmol) and Pd.sub.2(dba).sub.3 (233 mg, 0.25 mmol) added, and the mixture is refluxed under argon atmosphere overnight. The reaction mixture is cooled at room temperature, and the solid is removed by filtration. The filtrate is concentrated, and the crude product is chromatographed eluting with a mixed solvent of heptane and dichloromethane to yield 3.40 g (85%) of 10-3 as a beige powder. it is used for next reaction without further purification.

##STR00340##

[1023] 10-3 (1.45 g, 3.79 mmol), 1-4 (1.07 g, 4.20 mmol), and sodium tert-butoxide (510 mg, 5.31 mmol) are added to 55 mL of Toluene. The mixture is evacuated and purged with Argon gas three times. Then, 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (175 mg, 0.30 mmol) and Pd.sub.2(dba).sub.3 (174 mg, 0.19 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 7 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene. The crude product is chromatographed eluting with a mixed solvent of heptane and dichloromethane to yield 1.58 g (70%) of Compound 10 as a yellow powder.

[1024] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 9.21-9.17 (m, 2H), 8.95-8.76 (m, 2H), 8.43-8.23 (m, 1H), 8.13-7.72 (m, 5H), 7.67-7.20 (m, 9H), 7.05-6.72 (m, 5H)

[1025] LC-MS (m/z): 601 [M+1]

##STR00341##

[1026] 1,3-Dichloro-2-nitrobenzene (5.07 g, 26.54 mmol), dibenzofurane-4-boronic acid (5.628 g, 26.54 mmol), Pd(PPh.sub.3).sub.4 (610 mg, 0.53 mmol), and Na.sub.2CO.sub.3 (8.51 g, 80.29 mmol) are added to 25 mL of toluene, 5 mL of 1,2-dimethoxyethane, and 5 mL of water. The mixture is refluxed for 12 h. After the reaction mixture is cooled to room temperature, the aqueous layer is extracted with toluene. After the organic layer is dried with MgSO4, the solvent is evaporated. The crude product is chromatographed to yield 6.1 g (71%) of 11-1 as a white solid.

##STR00342##

[1027] 11-1 (1.98 g, 6.15 mmol) and triphenyl phosphine (4.06 g, 15.49 mmol) are added to 50 mL of 1,2-dichlorobenzene, and the mixture is stirred at 180? C. for 12 h. The reaction mixture is cooled to room temperature. The crude product is chromatographed to yield 1.2 g (67%) of 11-2 as a white solid.

##STR00343##

[1028] 11-2 (2.6 g, 8.93 mmol), bispinacolate diboron (6.8 g, 26.78 mmol), Pd.sub.2(dba).sub.3 (246 mg, 0.26 mmol), 2-dicyclohexylphosphino-2,4,6-triisopropylbiphenyl (248 mg, 0.52 mmol), and potassium acetate (256 mg, 2.6 mmol) are added to 45 mL of 1,4-dioxane. The mixture is refluxed for 12 h. After the reaction mixture is cooled to room temperature, the solvent is evaporated. The crude product is chromatographed to yield 2.5 g (74%) of 11-3 as a white solid.

##STR00344##

[1029] 11-3 (2.52 g, 6.53 mmol), 2-bromonitrobenzene (1.31 g, 6.53 mmol), Pd(PPh.sub.3).sub.4 (130 mg, 0.53 mmol), and Na.sub.2CO.sub.3 (1.93 g, 19.75 mmol) are added to 15 mL of toluene, 3 mL of 1,2-dimethoxyethane, and 3 mL of water under argon atmosphere. The mixture is refluxed for 12 h. After the reaction mixture is cooled to room temperature, the aqueous layer is extracted with toluene. After the organic layer is dried with MgSO4, the solvent is evaporated. The crude product is chromatographed to yield 2.0 g (81%) of 11-4 as a pale yellow solid.

##STR00345##

[1030] 11-4 (2.00 g, 5.30 mmol), bromobenzene (827 mg, 5.30 mmol), and sodium tert-butoxide (713 mg, 7.42 mmol) are added to 30 mL of Toluene. The reaction mixture is evacuated and purged with argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (123 mg, 0.42 mmol) and Pd.sub.2(dba).sub.3 (98 mg, 0.11 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. overnight. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is purified by sublimation to yield 1.30 g (54%) of 11-5 as a pale yellow powder.

##STR00346##

[1031] 11-5 (1.98 g, 6.15 mmol) and triphenyl phosphine (4.06 g, 15.49 mmol) are added to 50 mL of 1,2-dichlorobenzene, and the mixture is stirred at 180? C. for 12 h. The reaction mixture is cooled to room temperature. The crude product is chromatographed to yield 262 mg (62%) of 11-6 as a white solid.

##STR00347##

[1032] 1-4 (1.40 g, 5.50 mmol), 11-6 (2.10 g, 5.00 mmol), and sodium tert-butoxide (673 mg, 7.00 mmol) are added to 60 mL of Toluene. The mixture is evacuated and purged with argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (116 mg, 0.40 mmol) and Pd.sub.2(dba).sub.3 (92 mg, 0.10 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. overnight. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is purified by sublimation to yield 2.30 g (72%) of Compound 11 as a yellow powder.

[1033] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 8.92-8.85 (m, 2H), 8.69-8.60 (m, 1H), 8.50-8.40 (m, 1H), 8.18-8.05 (m, 2H), 7.99 (t, J=8.2 Hz, 1H), 7.81 (ddd, J=8.8, 7.3, 1.7 Hz, 1H), 7.74-7.29 (m, 11H), 6.75 (br, 5H)

[1034] LC-MS (m/z): 640 [M]

##STR00348##

[1035] 3-Bromo-2-nitroaniline (21.70 g, 100.0 mmol), dibenzofurane-4-boronic acid (21.20 g, 100.0 mmol) and potassium phosphate (42.45 g, 200.0 mmol) are dissolved in 200 mL of tetrahydrofuran and 50 mL of water. The reaction mixture is evacuated and purged with argon gas three times. Tri-t-butylphosphoniumtetrafluoroborat (290 mg, 1.0 mmol) and Pd.sub.2(dba).sub.3 (458 mg, 0.5 mmol) are added and the mixture is refluxed for 1.5 h. After cooling to room temperature, 200 mL of water and 200 mL of toluene are added and the reaction mixture is filtered. The filtrate is transferred to a separation funnel, the phases are separated and the aqueous layer is extracted with toluene. The organic layer is washed with brine, dried with Na.sub.2SO.sub.4 and the solvent is evaporated. The crude product is chromatographed with heptane/toluene as eluent to yield 29.57 g (97%) of 12-1 as a solid.

##STR00349##

[1036] 12-1 (13.99 g, 46.0 mmol) and cesium carbonate (29.97 g, 92.0 mmol) are suspended in 150 mL of toluene and evacuated and purged with argon. 1-Bromo-2-chlorobenzene (8.81 g, 46.0 mmol) is added, then argon is bubbled through for 15 minutes. Rac-BINAP (859 mg, 1.38 mmol) and Pd.sub.2(dba).sub.3 (842 mg, 0.92 mmol) are added and the reaction mixture is refluxed for 15 hours. After cooling to room temperature the suspension is filtered and the filtrate is evaporated. The crude product is chromatographed with heptane/toluene as eluent to yield 17.40 g (91%) of 12-2 as a solid.

##STR00350##

[1037] 12-2 (415 mg, 1.00 mmol) and potassium carbonate (276 mg, 2.00 mmol) are suspended in 8 mL of o-xylene and evacuated and purged with argon. Then argon is bubbled through for 15 minutes. Tricyclohexylphosphine (34 mg, 0.12 mmol) and palladium(III)acetate (13 mg, 0.06 mmol) are added and the reaction mixture is refluxed for 21 hours. After cooling to room temperature the suspension is filtered and the filtrate is evaporated. The crude product is chromatographed with heptane/toluene as eluent to yield 216 mg (57%) of 12-3 as a solid.

##STR00351##

[1038] 12-3 (5.11 g, 13.50 mmol), iodobenzene (12.39 g, 60.75 mmol), copper (642 mg, 10.10 mmol) and potassium carbonate (5.59 g, 40.50 mmol) are suspended in 55 mL of nitrobenzene. The reaction mixture is stirred at 200? C. for 43 hours, then cooled to room temperature and the solvent is evaporated in vacuo. The residue is stirred with 100 mL of water and 130 mL of toluene and filtered. The filtrate is transferred to a separation funnel and the phases are separated. The water phase is extracted with toluene, the organic phase is washed with brine, dried with Na.sub.2SO.sub.4, filtered and the solvent is evaporated. The crude product is chromatographed with heptane/toluene as eluent to yield 4.97 g (81%) of 12-4 as a solid.

##STR00352##

[1039] 12-4 (4.99 g, 11.00 mmol) and triphenyl phosphine (43.28 g, 165.0 mmol) are mixed and heated to 200? C. The solution is stirred at 200? C. for 64 hours, then cooled to room temperature. The brown solid is chromatographed with heptane/toluene as eluent to yield 3.96 g (85%) of 12-5 as a solid.

##STR00353##

[1040] 1-4 (1.17 g, 4.60 mmol), 12-5 (1.69 g, 4.00 mmol) and sodium tert-butoxide (589 mg, 6.00 mmol) are suspended in 30 mL of toluene. The mixture is evacuated and purged with argon, then argon is bubbled through for 15 minutes. 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (139 mg, 0.24 mmol) and Pd.sub.2(dba).sub.3 (110 mg, 0.12 mmol) are added and the reaction mixture is refluxed for 1 h. After cooling to room temperature, 100 mL of water and 30 mL of toluene are added and the reaction mixture is filtered. The filtrate is transferred to a separation funnel and the phases are separated. The water phase is extracted with toluene, the organic phase is washed with brine, dried with Na.sub.2SO.sub.4, filtered and the solvent is evaporated. The crude product is chromatographed with heptane/toluene as eluent to yield 2.33 g (91%) of compound 12 as a yellow solid.

[1041] LC-MS (m/z): 640 [M]

##STR00354##

[1042] 1-4 (1.40 g, 5.50 mmol), 6-phenyl-5,6-dihydrobenzofuro[2,3-c]indolo[2,3-a]carbazole (2.10 g, 5.00 mmol), and sodium tert-butoxide (673 mg, 7.00 mmol) are added to 50 mL of Toluene. The mixture is evacuated and purged with Argon gas three times. Then, 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (231 mg, 0.40 mmol) and Pd.sub.2(dba).sub.3 (230 mg, 0.25 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. overnight. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is purified by column chromatography by eluting with a mixed solvent of heptane and dichloromethane to yield 1.94 g (60%) of Compound 13 as a yellow powder.

[1043] LC-MS (m/z): 641 [M+1]

##STR00355##

[1044] 1-4 (1.50 g, 5.87 mmol), 9-phenyl-9H,9H-2,3-bicarbazole (2.00 g, 4.90 mmol), and sodium tert-butoxide (659 mg, 6.85 mmol) are added to 33 mL of Toluene. The mixture is evacuated and purged with Argon gas three times. The reaction mixture is evacuated and purged with Argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (114 mg, 0.39 mmol) and Pd.sub.2(dba).sub.3 (90 mg, 0.10 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 17 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is recrystallized with chloroform and ethanol to yield 3.02 g (98%) of Compound 14 as a yellow powder.

[1045] .sup.1H NMR (300 MHz, CDCl.sub.3) ? 9.14-9.04 (m, 2H), 8.67 (dd, J=8.0, 1.7 Hz, 1H), 8.36 (dd, J=1.9, 0.6 Hz, 1H), 8.28 (dd, J=8.1, 0.7 Hz, 1H), 8.24-8.14 (m, 2H), 7.96-7.84 (m, 2H), 7.80-7.67 (m, 7H), 7.66-7.31 (m, 9H), 7.21 (dd, J=8.0, 0.8 Hz, 1H)

[1046] LC-MS (m/z): 627 [M+1]

##STR00356##

[1047] 1-4 (1.01 g, 3.97 mmol), 9-phenyl-9H,9H-2,2-bicarbazole (1.35 g, 3.31 mmol), and sodium tert-butoxide (445 mg, 4.63 mmol) are added to 22 mL of Toluene. The mixture is evacuated and purged with Argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (77 mg, 0.26 mmol) and Pd.sub.2(dba).sub.3 (61 mg, 0.07 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. overnight. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is recrystallized with chloroform and ethanol to yield 1.69 g (67%) of Compound 15 as a yellow powder.

[1048] LC-MS (m/z): 627 [M+1]

##STR00357##

[1049] 16-0 (3.00 g, 8.40 mmol) which prepared according to the procedure mentioned in WO2011086941, 2-chloroaniline (1.07 g, 8.40 mmol), and sodium tert-butoxide (1.61 g, 16.80 mmol) are added to 20 mL of toluene. The mixture is evacuated and purged with Argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (244 mg, 0.84 mmol) and Pd.sub.2(dba).sub.3 (384 mg, 0.42 mmol) are added to the mixture, and the reaction mixture is refluxed overnight. The reaction mixture is cooled to room temperature, and diluted with chloroform. The solid is removed by filtration, and the crude product is chromatographed eluting with a mixed solvent of heptane and dichloromethane to yield 2.47 g (80%) of 16-1 as a beige powder.

[1050] LC-MS (m/z): 369 [M+1]

##STR00358##

[1051] 16-1 (1.47 g, 4.00 mmol), 1-4 (1.22 g, 4.80 mmol), and sodium tert-butoxide (538 mg, 5.60 mmol) are added to 27 mL of toluene. The mixture is evacuated and purged with Argon gas three times. Then, 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (93 mg, 0.16 mmol) and Pd.sub.2(dba).sub.3 (73 mg, 0.07 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. overnight. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is recrystallized with chloroform and ethanol to yield 2.33 g (99%) of Compound 16 as a yellow powder.

[1052] .sup.1H NMR (300 MHz, CDCl.sub.3) ? 9.14-9.06 (m, 1H), 8.94-8.86 (m, 1H), 8.81-8.74 (m, 2H), 8.52 (td, J=8.1, 1.0 Hz, 1H), 8.25 (d, J=7.9 Hz, 1H), 8.21-8.10 (m, 2H), 8.05-7.94 (m, 3H), 7.89-7.59 (m, 7H), 7.51 (ddd, J=8.4, 6.9, 1.3 Hz, 1H), 7.44-7.36 (m, 2H), 7.35-7.18 (m, 2H)

[1053] LC-MS (m/z): 586 [M+1]

##STR00359##

[1054] 1-4 (1.77 g, 6.95 mmol), 7,7-dimethyl-5,7-dihydroindeno[2,1-b]carbazole (1.79 g, 6.32 mmol), and sodium tert-butoxide (850 mg, 8.84 mmol) are added to 50 mL of Toluene. The mixture is evacuated and purged with Argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (147 mg, 0.51 mmol) and Pd.sub.2(dba).sub.3 (116 mg, 0.13 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 4 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with toluene and ethanol. The crude product is recrystallized with chloroform and heptane to yield 1.8 g (57%) of Compound 17 as a yellow powder.

[1055] .sup.1H NMR (300 MHz, DMSO-d.sub.6) ? 9.09 (d, J=2.6 Hz, 1H), 8.97 (dd, J=8.3, 2.8 Hz, 1H), 8.63 (d, J=3.4 Hz, 1H), 8.26 (dd, J=8.0, 2.6 Hz, 1H), 8.03-7.88 (m, 2H), 7.83-7.67 (m, 1H), 7.67-7.31 (m, 8H), 7.25-7.23 (br, 1H), 1.61 (s, 6H)

[1056] LC-MS (m/z): 501 [M]

##STR00360##

[1057] 9-Bromo-7,7-domethyl-7H-benzo[c]fluorene (10.70 g, 33.10 mmol), 2-chloroaniline (4.23 g, 33.10 mmol), and sodium tert-butoxide (9.34 g, 66.20 mmol) are added to 110 mL of toluene. The mixture is evacuated and purged with Argon gas. Then, .sup.tBu.sub.3PHBF.sub.4 (418 mg, 1.44 mmol) and Pd.sub.2(dba).sub.3 (659 mg, 0.72 mmol) are added to the mixture, and the reaction mixture is stirred at 110? C. for 1 h. The reaction mixture is cooled at room temperature, and diluted with toluene. The solid is removed by filtration, and the filtrate is concentrated. The crude product is chromatographed eluting with a mixed solvent of heptane and toluene to yield 4.44 g (36%) of 18-1 as a beige powder and 6.21 g (56%) of 18-2 as a beige powder.

##STR00361##

[1058] 18-1 (6.2 g, 13.95 mmol) and potassium carbonate (4.65 g, 33.65 mmol) are suspended in 90 mL of dimethylacetamide. To the suspension are PCy.sub.3-HBF.sub.4 (248 mg, 0.67 mmol) and Pd(OAc).sub.2 (62 mg, 0.27 mmol) added, and the mixture is stirred at 135? C. for 4.5 h. The reaction mixture is cooled at room temperature, and the solid is removed by filtration. The filtrate is concentrated, and the crude product is purified by recrystallization with a mixed solvent of heptane and ethyl acetate to yield 3.54 g (63%) of 18-2 as a beige powder.

##STR00362##

[1059] 1-4 (2.80 g, 11.00 mmol), 18-2 (3.33 g, 10.00 mmol) and sodium tert-butoxide (1.06 g, 11.00 mmol) are added in 50 mL of toluene. The mixture is evacuated and purged with argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (232 mg, 0.80 mmol) and Pd.sub.2(dba).sub.3 (183 mg, 0.20 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for 17 h. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with methanol. The crude product is recrystallized with dimethylsulfoxide under nitrogen atmosphere to yield 4.27 g (78%) of Compound 18 as a yellow powder.

[1060] .sup.1H NMR (300 MHz, CDCl.sub.3) ? 9.21 (s, 1H), 9.13-9.06 (m, 1H), 9.04-9.02 (m, 2H), 8.77-8.69 (m, 1H), 8.36-8.29 (m, 1H), 8.02 (dd, J=8.3, 1.3 Hz, 1H), 7.98-7.85 (m, 2H), 7.83-7.67 (m, 4H), 7.63-7.57 (m, 2H), 7.54-7.41 (m, 3H), 7.24 (dd, J=8.1, 0.8 Hz, 1H)), 1.75 (s, 6H)

[1061] LC-MS (m/z): 551 [M]

##STR00363##

[1062] 1-4 (0.64 g, 2.52 mmol), 2-(9H-carbazol-3-yl).sub.5-phenyl-5H-benzo[b]carbazole (1.05 g, 2.29 mmol), and sodium tert-butoxide (308 mg, 3.2 mmol) are added to 23 mL of Toluene. The mixture is evacuated and purged with argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (53 mg, 0.18 mmol) and Pd.sub.2(dba).sub.3 (42 mg, 0.05 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for overnight. The reaction mixture is cooled to room temperature. Then a solid is collected by filtration, and washed with methanol. The crude product is recrystallized with chloroform and ethanol to yield 1.45 g (94%) of Compound 19 as a yellow powder.

[1063] .sup.1H NMR (300 MHz, CDCl.sub.3) ? 9.17-9.06 (m, 2H), 8.73 (d, J=1.3 Hz, 1H), 8.70-8.61 (m, 2H), 8.42 (dd, J=2.0, 0.6 Hz, 1H), 8.21 (ddd, J=7.7, 1.3, 0.6 Hz, 1H), 8.16-8.08 (m, 1H), 8.00-7.83 (m, 4H), 7.82-7.36 (m, 15H), 7.17 (dd, J=8.0, 0.8 Hz, 1H)

[1064] LC-MS (m/z): 677 [M+1]

##STR00364##

[1065] 3-Bromocarbazole (7.87 g, 32.00 mmol), [9-(2-naphthyl)carbazole-3-yl]boronic acid (11.33 g, 33.60 mmol) and potassium phosphate (16.98 g, 80.00 mmol) are dissolved in 120 mL of tetrahydrofuran and 30 mL of water. The mixture is evacuated and purged with argon, then argon is bubbled through for 15 minutes. Tri-t-butylphosphoniumtetrafluoroborat (371 mg, 1.28 mmol) and Pd.sub.2(dba).sub.3 (586 mg, 0.64 mmol) are added and the mixture is refluxed for 2 hours. After cooling to room temperature, 100 mL of water are added and the reaction mixture is filtered. The filtrate is transferred to a separation funnel and the product is extracted twice with toluene. The organic layer is washed with brine, dried with Na.sub.2SO.sub.4 and the solvent is evaporated. The crude product is suspended in THF and heated to reflux for 15 minutes, then cooled to room temperature, filtered and the residue dried in vacuo to yield 9.84 g (67%) of 20-1 as a white powder.

[1066] LC-MS: 458 [M]

##STR00365##

[1067] 1-4 (1.54 g, 6.05 mmol), 20-1 (2.52 g, 5.50 mmol) and sodium tert-butoxide (809 mg, 8.25 mmol) are suspended in 50 mL of toluene. The mixture is evacuated and purged with argon, then argon is bubbled through. 4,5-Bis(diphenylphosphino)-9,9-dimethylxanthene (127 mg, 0.22 mmol) and Pd.sub.2(dba).sub.3 (101 mg, 0.11 mmol) are added and the reaction mixture is heated to 80? C. for 2 hours. After cooling to room temperature, the solid is collected by filtration and washed with toluene and ethanol. The crude product is crystallized from chlorobenzene to yield 2.57 g (69%) of compound 20 as a yellow solid.

[1068] .sup.1H NMR (300 MHz, CDCl.sub.3) ? 9.10-9.07 (m, 2H), 8.58 (dd, J=7.9, 1.7 Hz, 1H), 8.54 (d, J=1.8 Hz, 1H), 8.37 (d, J=1.9 Hz, 1H), 8.30 (dd, J=7.7, 1.0 Hz, 1H), 8.17 (dd, J=7.8, 1.3 Hz, 1H), 8.13-8.11 (m, 2H), 8.02 (dt, J=7.0, 3.6 Hz, 1H), 7.96 (dt, J=7.0, 3.4 Hz, 1H), 7.90 (dd, J=8.7, 2.0 Hz, 1H), 7.84-7.82 (m, 2H), 7.75 (dd, J=8.7, 2.0 Hz, 1H), 7.68-7.32 (m, 12H), 7.11 (d, J=8.0 Hz, 1H)

[1069] LC-MS (m/z): 676 [M]

##STR00366##

[1070] Phenylhydrazine hydrochloride (8.03 g, 55.5 mmol) is dissolved in 280 ml of EtOH and 32 mL of acetic acid. The mixture is stirred at 80? C. for 15 min. After that, 6-Bromo-2-tetralone (12.5 g, 55.5 mmol) is added dropwise to the solution, and the mixture is stirred at 85? C. for 20 hours. The reaction mixture is evaporated to remove EtOH. 100 ml of H.sub.2O is added to the resulting solution, which is filtrated to give a crude material. The crude material is purified by column chromatography by eluting with a mixed solvent of heptane and dichloromethane, and is then washed with Hexane to yield 11.7 g (71%) of 21-1 as a white powder.

[1071] LC-MS (m/z): 298 [M+1]

##STR00367##

[1072] 21-1 (11.7 g, 39.2 mmol) and chloranil (13.5 g, 54.9 mmol) are added to 80 mL of Xylene. The resulting mixture is stirred at 130? C. for 20 hours. The reaction mixture is cooled at room temperature and is then filtered through a pad of celite washing well with CH.sub.2Cl.sub.2. The resulting solution is evaporated to give a crude material. The crude material is purified by CombiFlash eluting with a mixed solvent of heptane and dichloromethane, and is then washed with Hexane to yield 9.87 g (85%) of 21-2 as a white solid.

[1073] LC-MS (m/z): 296 [M+1]

##STR00368##

[1074] 21-2 (8.00 g, 27.0 mmol), iodobenzene (11.0 g, 54.0 mmol), CuI (5.14 g, 54.0 mmol), K.sub.3PO.sub.4 (11.5 g, 54.0 mmol) and cyclohexanediamine (6.17 g, 54.0 mmol) are added in 135 mL of 1,4-dioxane, and degassed under N.sub.2 for 5 minutes. The mixture is heated at 115? C. for 24 hours. The reaction mixture is cooled to room temperature and is then filtered through a pad of celite washing well with ethyl acetate. The filtrate is evaporated to give a crude material as a black oil. The crude product i purified by CombiFlash eluting with a mixed solvent of heptane and dichloromethane, and is then washed with Hexane to yield 5.56 g (55%) of 21-3 as a white solid.

[1075] LC-MS (m/z): 372 [M+1]

##STR00369##

[1076] 21-3 (5.50 g, 14.8 mmol) is combined with 3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole (3.91 g, 13.3 mmol), Pd(dppf)Cl.sub.2 (0.604 g, 0.740 mmol), and 2M Na.sub.2CO.sub.3 aq. (14 ml) in Toluene/EtOH (30 ml, 2:1 mixed solution) and degassed under N.sub.2 for 5 minutes. The resulting mixture is heated at 90? C. for 12 hours. The reaction mixture is cooled to room temperature and is then filtered through a pad of celite washing well with dichloromethane. The resulting solution is evaporated to give a crude material as a black oil. The crude material is purified by CombiFlash eluting with a mixed solvent of heptane and dichloromethane, and is then washed with methanol to yield 4.25 g (70%) of 21-4 as a white solid.

[1077] LC-MS (m/z): 459 [M+1]

##STR00370##

[1078] 21-4 (2.35 g, 5.12 mmol), 1-4 (1.10 g, 4.32 mmol), and sodium tert-butoxide (984 mg, 10.2 mmol) are added to 25 mL of xylene. The mixture is evacuated and purged with argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (297 mg, 1.02 mmol) and Pd.sub.2(dba).sub.3 (234 mg, 0.256 mmol) are added to the mixture, and the reaction mixture is stirred at 130? C. for 24 h. The reaction mixture is cooled to room temperature and is then filtered through a pad of celite washing well with THF. The filtrate is evaporated to give a crude material as a black oil. The crude material is purified by CombiFlash eluting with a mixed solvent of heptane and THF, and is then washed with MeOH to yield 2.50 g (72%) of compound 21 as a yellow solid.

[1079] LC-MS (m/z): 677 [M+1]

##STR00371##

[1080] 2-Amino-6-nitrobenzoic acid (8.38 g, 46.00 mmol) is dissolved in 35 mL of sulfuric acid, and the solution is cooled at 5? C. To the solution is a solution of 4.4 g of sodium nitrite dissolved in 26 mL of water added dropwise. The reaction mixture is then poured into a stirred solution of benzenethiol ([4.97 g, 45.08 mmol] in 85 mL of 35% NaOH solution), and the mixture is stirred at 95? C. overnight. The reaction mixture is extracted with toluene, and the aqueous layer is acidified with conc. HCl. Then, it is extracted with ethyl acetate, and the organic layer is evaporated after it is dried with MgSO.sub.4. The crude is purified by column chromatography by eluting with a mixed solvent of toluene, ethanol, and acetic acid to yield 5.66 g (41%) of the intermediate 22-1. It is used for next reaction without further purification.

##STR00372##

[1081] 22-1 (5.77 g, 20.96 mmol) is suspended in poly phosphoric acid (42 g) and 14 mL of acetic acid, and the mixture is stirred at 140? C. for 1 h. The reaction mixture is poured into ice water and basified with 50% NaOH solution. The formed solid is collected by filtration, and washed out with chloroform. After the filtrated is concentrated, the crude product is purified by column chromatography by eluting with chloroform to yield 1.17 g (22%) of the intermediate 222.

[1082] LC-MS (m/z) 258

##STR00373##

[1083] 22-2 (1.6 g, 6.13 mmol) is suspended in 25 mL of acetic acid, and the mixture is heated to 50? C. To this mixture are iron (1.74 g, 31.10 mmol) and 6 mL of water, and then the mixture is stirred at 100? C. for 35 min. After the reaction mixture is cooled at room temperature, it is basified with 2 M Na.sub.2CO.sub.3, and extracted with chloroform. After the organic layer is dried with Na2SO4, it is concentrated. The crude product is purified by column chromatography by eluting with chloroform to yield 1.74 g (92%) of the intermediate 22-3.

[1084] LC-MS (m/z) 228

##STR00374##

[1085] 22-3 (1.61 g, 7.08 mmol) is suspended in 71 mL of acetic acid and 6 mL of water. Sodium cyanate (0.69 g, 10.63 mmol) is added there, and the mixture is stirred at room temperature for 45 min. The reaction mixture is diluted with 142 mL of water to give a solid. The solid is collected by filtration to yield 1.74 g (85%) of the intermediate 23-4. It is used for the next reaction without further purification.

##STR00375##

[1086] 22-4 (1.74 g, 6.44 mmol) is suspended in 805 mL of ethanol and potassium hydroxide (0.80 g, 14.16 mmol) is added. The mixture is stirred at 85? C. for 35 min. The reaction mixture is cooled at room temperature, and 14 mL of 1N HCl is added. Then, the solvent is evaporated to give the intermediate 22-5. The crude product is used for the next reaction without purification.

##STR00376##

[1087] 22-5 (1.63 g, 6.47 mmol) is suspended in 24 mL of toluene, and heated at 50? C. Phosphoryl chloride (7.44 g, 48.52 mmol) is added dropwise, and then DBU (1.97 g, 12.94 mmol) is added dropwise there. The mixture is refluxed overnight. The reaction mixture is cooled at room temperature, and poured into ice water. The mixture is stirred for 30 min. The aqueous layer is extracted with CHCl3. The organic layer is washed with brine, dried with Na2SO4, and then the solvent is evaporated. The crude product is purified by column chromatography by eluting with chloroform to yield 901 mg (51%) of the intermediate 22-6.

[1088] LC-MS (m/z) 271/273

##STR00377##

[1089] 23-6 (898 mg, 3.32 mmol), 3-(9H-carbazol-3-yl)-9-phenyl-carbazole (1.36 g, 3.32 mmol), and sodium tert-butoxide (446 mg, 4.64 mmol) are added to 27 mL of Toluene. The mixture is evacuated and purged with argon gas three times. Then, .sup.tBu.sub.3PHBF.sub.4 (77 mg, 0.27 mmol) and Pd.sub.2(dba).sub.3 (61 mg, 0.06 mmol) are added to the mixture, and the reaction mixture is stirred at 80? C. for over the weekend. The reaction mixture is cooled to room temperature, and the solid is collected by filtration. The solid is washed out with toluene and ethanol. It is purified by flash chromatography eluting with a mixed solvent of heptane and chloroform to yield 1.09 g (51%) of Compound 22 as a yellow powder.

[1090] .sup.1H NMR (300 MHz, DMSO-d.sub.6) b 9.01-8.86 (m, 3H), 8.81-8.67 (m, 2H), 8.42-8.40 (m, 2H), 8.04 (dd, J=8.8, 2.0 Hz, 1H), 8.00-7.88 (m, 2H), 7.82-7.55 (m, 11H), 7.55-7.41 (m, 4H), 7.37-7.35 (m, 1H)

[1091] LC-MS (m/z): 677 [M+1]

Further Application Examples

Application Example 4

[1092] According to Application Example 1, Application example 4 is repeated except that the host (Compound 1) is replaced by Compound 3. The device result is shown in Table 3.

Comparative Application Example 1

[1093] According to Application Example 1, Comparative application example 1 is repeated except that the host (Compound 1) is replaced by Comparative 2. The device result is shown in Table 3.

##STR00378##

[1094] OLED Characterization

[1095] To characterize the OLED, electroluminescence spectra are recorded at various currents and voltages. In addition, the current-voltage characteristic is measured in combination with the luminance to determine luminous efficiency and external quantum efficiency (EQE). Driving voltage U, EQE, Commission Internationale de l'?clairage (CIE) coordinate are given at 10 mA/cm.sup.2 except otherwise stated.

TABLE-US-00003 TABLE 3 Appl. Ex. Host U (V) EQE (%) CIE x, y Appl. Ex. 4 Compound 3 4.93 15.0 0.67, 0.33 Comp. Appl. Ex. 1 Comparative 2 5.30 13.8 0.66, 0.33

[1096] The results are shown in Table 3. The CIE values show that the electroluminescence is originated from the red emitter compound (Compound D). Compound 3 can show lower driving voltage and higher EQE than Comparative 2.

Application Example 5

[1097] According to Application Example 1, Application Example 5 is repeated except that the hole transporting layer is replaced by 210 nm-thick of Compound B as the first layer and 10 nm-thick of Compound B as the second layer.

##STR00379##

Application Examples 6 to 21

[1098] According to Application Example 5, Application Examples 6 to 21 are repeated except that the host (Compound 1) is replaced by Compound 6 to 13 and 15 to 22. The device results are shown in Table 4.

Comparative Application Example 2

[1099] According to Application Example 5, Comparative application example 2 is repeated except that the host (Compound 1) is replaced by Comparative 1. The device result is shown in Table 4.

TABLE-US-00004 TABLE 4 Appl. Ex. Host U (V) CIE (x, y) Appl. Ex. 5 Compound 1 5.36 0.66, 0.33 Appl. Ex. 6 Compound 6 4.52 0.66, 0.33 Appl. Ex. 7 Compound 7 4.52 0.66, 0.33 Appl. Ex. 8 Compound 8 5.13 0.66, 0.33 Appl. Ex. 9 Compound 9 4.89 0.66, 0.33 Appl. Ex. 10 Compound 10 4.89 0.66, 0.33 Appl. Ex. 11 Compound 11 5.08 0.66, 0.33 Appl. Ex. 12 Compound 12 5.11 0.66, 0.33 Appl. Ex. 13 Compound 13 4.66 0.66, 0.33 Appl. Ex. 14 Compound 15 5.40 0.66, 0.33 Appl. Ex. 15 Compound 16 4.88 0.66, 0.33 Appl. Ex. 16 Compound 17 5.11 0.66, 0.33 Appl. Ex. 17 Compound 18 4.88 0.66, 0.33 Appl. Ex. 18 Compound 19 4.68 0.66, 0.33 Appl. Ex. 19 Compound 20 5.12 0.66, 0.33 Appl. Ex. 20 Compound 21 5.10 0.66, 0.33 Appl. Ex. 21 Compound 22 5.34 0.66, 0.33 Comp. Appl. Ex. 2 Comparative 1 5.42 0.66, 0.34

[1100] The results are shown in Table 4. The CIE values show that the electroluminescence is originated from the red emitter compound (Compound D). The results of Table 4 demonstrate that the new compounds listed on the table show lower driving voltage than Comparative 1.