Cyclic azine derivatives, processes for producing these, and organic electroluminescent element containing these as component

1. A cyclic azine compound represented by the formula (1)

wherein, in the formula (1), each Ar 1 represents a phenyl, naphthyl or pyridyl group which are unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms, a phenyl group or a pyridyl group; and A represents a group selected from the group consisting of those which are represented by the following formulae (3) to (5):

wherein, in the formula (3), Ar a represents a phenyl group, a pyridyl group or a pyrimidyl group; Ar 4 represents an anthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a phenanthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a fluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a benzofluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, an unsubstituted pyrenyl group, an unsubstituted triphenylenyl group; X represents a phenylene group or a pyridylene group; p represents an integer of 0 to 2 provided that, when p is 2, the two Xs may be the same or different; and Z 1 represents a nitrogen atom;

wherein, in the formula (4), each Ar 5 represents a pyridyl group, and each Ar 6 represent a phenyl group or a pyridyl group; Z 2 represents a nitrogen atom and each Z 3 represents a carbon atom or a nitrogen atom,

wherein, in the formula (5), each Ar 4 independently represents an anthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a phenanthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a fluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a benzofluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, an unsubstituted pyrenyl group, an unsubstituted triphenylenyl group.

2. The cyclic azine compound according to claim 1 , wherein each Ar 4 in the formula (5) represents an anthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a phenanthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a fluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, an unsubstituted pyrenyl group, or an unsubstituted triphenylenyl group.

3. A process for preparing a cyclic azine compound represented by the formula (1b):

wherein, in the formula (1b), each Ar 1 represents a phenyl, naphthyl or pyridyl group which are unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms, a phenyl group or a pyridyl group; Ar 3 represents a phenyl group, a pyridyl group or a pyrimidyl group; Ar 4 represents an anthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a phenanthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a fluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a benzofluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, an unsubstituted pyrenyl group, an unsubstituted triphenylenyl group; X represents a phenylene group or a pyridylene group; p represents an integer of 0 to 2 provided that, when p is 2, the two Xs may be the same or different; and Z 1 represents a nitrogen atom; characterized by coupling a compound represented by the formula (10) with a compound represented by the formula (11) in the presence of a palladium catalyst and in the presence or absence of a base;

wherein, in the formula (10), each Ar 1 is the same as defined above; Ar 4 is the same as defined above; Z 1 represents a nitrogen atom; and Y 1 represents a chlorine, bromine or iodine atom;

Ar 3 -Xp-M  (11)

wherein, in the formula (11), Ar 3 represents a phenyl group, a pyridyl group or a pyrimidyl group; X represents a phenylene group or a pyridylene group; p represents an integer of 0 to 2 provided that, when p is 2, the two Xs may be the same or different; and M represents a metal group or a hetero atom group.

4. A process for preparing a cyclic azine compound represented by the formula (1c):

wherein, in the formula (1c), each Ar 1 represents a phenyl, naphthyl or pyridyl group which are unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms, a phenyl group or a pyridyl group; each Ar 5 represents a pyridyl group, and each Ar 6 represent a phenyl group or a pyridyl group; and Z 2 represents a nitrogen atom and each Z 3 represents a carbon or nitrogen atom; characterized by coupling a compound represented by the formula (12) with a compound represented by the formula (13) in the presence of a palladium catalyst and a base;

wherein, in the formula (12), each Ar 1 is the same as defined above; Z 2 represents a nitrogen atom; each R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; and groups R 1 in the two —B(OR 1 ) 2 groups may be the same or different, and two groups R 1 in each of the two —B(OR 1 ) 2 groups may form a ring together with the oxygen atoms and the boron atom;

wherein, in the formula (13), Ar 5 is the same as defined above, and Ar 6 is the same as defined above; and Z 3 represents a carbon or nitrogen atom; and Y 1 represents a chlorine, bromine or iodine atom.

5. A process for preparing a cyclic azine compound represented by the formula (1d):

wherein, in the formula (1d), each Ar 1 represents an aromatic group, which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms, a phenyl group or a pyridyl group; and each Ar 4 independently represents an unsubstituted or substituted aromatic hydrocarbon group having 2 to 4 rings; characterized by coupling a compound represented by the formula (14) with a compound represented by the formula (15) in the presence of a palladium catalyst and a base;

wherein, in the formula (14), each Ar 1 represents a phenyl, naphthyl or pyridyl group which are unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms, a phenyl group or a pyridyl group; each R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; and groups R 1 in the two B(OR 1 ) 2 groups may be the same or different, and two groups R 1 in each of the two —B(OR 1 ) 2 groups may form a ring together with the oxygen atoms and the boron atom;

Ar 4 Y 1   (15)

wherein, in the formula (15), Ar 4 represents an anthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a phenanthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a fluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a benzofluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, an unsubstituted pyrenyl group, an unsubstituted triphenylenyl group; and Y 1 represents a chlorine, bromine or iodine atom.

6. An organic electroluminescent device comprising as a constituent a cyclic azine compound represented by the formula (1):

wherein, in the formula (1), each Ar 1 represents an aromatic group, which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms, a phenyl group or a pyridyl group; and A represents a group selected from the group consisting of those which are represented by the following formulae (3) to (5):

wherein, in the formula (3), Ar a represents a phenyl group, a pyridyl group or a pyrimidyl group; Ar 4 represents an anthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a phenanthryl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a fluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, a benzofluorenyl group which is unsubstituted or substituted by an alkyl group having 1 to 4 carbon atoms or a phenyl group, an unsubstituted pyrenyl group, an unsubstituted triphenylenyl group; X represents a phenylene group or a pyridylene group; p represents an integer of 0 to 2 provided that, when p is 2, the two Xs may be the same or different; and Z 1 represents a nitrogen atom;

wherein, in the formula (4), each Ar 5 represents a pyridyl group, and each Ar 6 represent a phenyl group or a pyridyl group; Z 2 represents a nitrogen atom and each Z 3 represents a carbon atom or a nitrogen atom; and

wherein, in the formula (5), each Ar 4 is the same as defined above.

7. The process for preparing a cyclic azine compound according to claim 3 , wherein the palladium catalyst has a tertiary phosphine as a ligand.

8. The process for preparing a cyclic azine compound according to claim 4 , wherein the palladium catalyst has a tertiary phosphine as a ligand.

9. The process for preparing a cyclic azine compound according to 5 , wherein the palladium catalyst has a tertiary phosphine as a ligand.

10. The process for preparing a cyclic azine compound according to claim 3 , wherein the metal group or the hetero atom group, represented by M in the formulae (7) and (11), is a group represented by the following formula:

—B(OR 1 ) 2 or —ZnR 2

wherein R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group; two groups R 1 in the group —B(OR 1 ) 2 may be the same or different and the two groups R 1 in the group —B(OR 1 ) 2 may form a ring together with the oxygen atoms and the boron atom; and R 2 represents a halogen atom.