Hetarylbenzene compounds

Details Hetarylbenzene compounds Hetarylbenzene compounds

2001-11-21

2003-01-28

McKane, Joseph K. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C548S518000, C549S059000, C549S472000

Reexamination Certificate

active

06512122

ABSTRACT:

BACKGROUND
Electroluminescent (EL) devices based on organic thin layers have recently attracted much attention because of their potential uses in large-area flat-panel displays and light-emitting diodes (LED). Organic LEDs have been made with both low molecular-weight organic materials and with polymers. The performance of these devices is significantly influenced by the charge balance between electrons and holes from opposite electrodes. The charge can be balanced by using a bilayer structure including a hole transporting layer and an electron transporting layer. One or both of these layers can be luminescent.
An important quality of organic EL materials is their durability, i.e., thermal and morphological stability. Thus, it is desirable that organic EL materials are not only light-emitting and hole transporting, but also robust.
SUMMARY
The hexasubstituted benzene compounds of the invention are useful as hole transporting, green-light-emitting molecules with high glass transition temperatures. These compounds have a number of qualities that make them useful in electroluminescence devices.
In one aspect, the invention features a method of preparing a compound of formula I:
Each of R
1
-R
6
is, independently,
Y is O, S, NH, or C(R
7
)═C(R
8
). Each of R
7
-R
11
is, independently, H, substituted or unsubstituted C
1-6
alkyl, substituted or unsubstituted C
2-6
alkenyl, substituted or unsubstituted C
2-6
alkynyl, substituted or unsubstituted C
6-20
aryl, or substituted or unsubstituted C
4-20
heteroaryl. Alternatively, each of R
7
-R
11
is OH, C
1-6
alkoxy, or N(R
12
)(R
13
). For N(R
12
)(R
13
), each of R
12
and R
13
is, independently, H, substituted or unsubstituted C
1-6
alkyl, substituted or unsubstituted C
2-6
alkenyl, substituted or unsubstituted C
2-6
alkynyl, or substituted or unsubstituted C
6-20
aryl. Each of R
7
-R
11
can also be NO
2
, CN, or CO
2
R
14
, in which R
14
is H or C
1-6
alkyl.
The method includes contacting a compound of formula II with a compound of formula III to form a compound of formula I. The compound of formula II is shown below:
In this compound, each of X
1
-X
6
is, independently, Br or I. The compound of formula III is shown below:
In this compound, Y and R
7
-R
11
are as defined above and Z is ZnCl or Sn(R
15
)(R
16
)(R
17
), in which each of R
15
-R
17
is, independently, C
1-6
alkyl.
In some preferred embodiments, Y is O, S, or NH; each of R
10
and R
11
is H; and/or R
9
is N(R
12
)(R
13
). Preferably, each of R
12
and R
13
is, independently, substituted or unsubstituted aryl; for example, each of R
12
and R
13
can be, independently, phenyl, tolyl, naphthyl, or pyrenyl. In other preferred embodiments, R
9
is carbazolyl. In other preferred embodiments, Y is C(R
7
)═C(R
8
). In still other preferred embodiments, each of R
15
-R
17
is methyl or butyl.
In another aspect, the invention features a method of forming a hexaarylbenzene; the method includes contacting a hexahalobenzene with a stannane. In preferred embodiments, the hexaarylbenzene is a hexakis-(heteroaryl)benzene. For example, the hexaaryylbenzene can be a hexakis-(thienyl)benzene, e.g., a hexakis-(carbazolylthienyl)benzene, or a hexakis-(aminothienyl)benzene, e.g., a hexakis-[(diarylamino)thienyl]benzene.
In another aspect, the invention features a compound of formula I
Each of R
1
-R
6
is, independently,
in which Y is O, S, or NH. Each of R
9
-R
11
is, independently, H, substituted or unsubstituted C
1-6
alkyl, substituted or unsubstituted C
2-6
alkenyl, substituted or unsubstituted C
2-6
alkynyl, substituted or unsubstituted C
6-20
aryl, or substituted or unsubstituted C
4-20
heteroaryl. Alternatively, each of R
9
-R
11
is OH, C
1-6
alkoxy, or N(R
12
)(R
13
). For N(R
12
)(R
13
), each of R
12
and R
13
is, independently, H, substituted or unsubstituted C
1-6
alkyl, substituted or unsubstituted C
2-6
alkenyl, substituted or unsubstituted C
2-6
alkynyl, or substituted or unsubstituted C
6-20
aryl. Each of R
9
-R
11
can also be NO
2
, CN, or CO
2
R
14
, in which R
14
is H or C
1-6
alkyl.
In some preferred embodiments, each of R
10
and R
11
is H. In other preferred embodiments, R
9
is N(R
12
)(R
13
), and each of R
12
and R
13
is, independently, substituted or unsubstituted aryl, e.g., phenyl, tolyl, naphthyl, or pyrenyl. In still other preferred embodiments, R
9
is carbazolyl.
Preferably, Y is S. For example, each of R
1
-R
6
can have one of the following formulae:
In another aspect, the invention features an electroluminescence device made with one of more of the compounds described above. The device includes a substrate, which may be coated. The device also includes a hole transporting layer, an emitting layer, and an electron transporting layer. The compounds described above may be included in the hole transporting layer and/or the emitting layer.
The term “saturated” used herein refers to a compound or portion of a compound having each atom either hydrogenated or substituted such that the valency of each atom is filled.
The term “unsaturated” used herein refers to a compound or portion of a compound where the valency of each atom may not be filled with hydrogen or other substituents. For example, adjacent carbon atoms can be doubly bound to each other.
The term “substituted” used herein refers to moieties having one, two, three or more substituents, which may be the same or different, each replacing a hydrogen atom. Examples of substituents include but are not limited to alkyl, hydroxyl, protected hydroxyl, amino, protected amino, carboxy, protected carboxy, cyano, alkoxy, and nitro.
The term “unsubstituted” used herein refers to a moiety having each atom hydrogenated such that the valency of each atom is filled.
The term “aryl” used herein refers to a moiety having a hydrocarbon ring system (e.g., a fused ring system) having at least one aromatic ring. Examples of aryl moieties include, but are not limited to, phenyl, naphthyl, and pyrenyl.
The term “heteroaryl” used herein refers to a moiety having a ring system (e.g., a fused ring system) with at least one aromatic ring and at least one heteroatom, including, but not limited to, O, N, and S. Examples of heteroaryl moieties include, but are not limited to, pyridinyl, carbazolyl, and indolyl.
Protected forms of the compounds described herein are included within the scope of the invention. In general, the species of protecting group is not critical, provided that it is stable to the conditions of any subsequent reaction(s) on other positions of the compound and can be removed at the appropriate point without adversely affecting the remainder of the molecule. In addition, one protecting group may be substituted for another after substantive synthetic transformations are complete. Examples and conditions for the attachment and removal of various protecting groups are found in T. W. Greene, Protective Groups in Organic Chemistry, (1st ed., 1981, 2nd ed., 1991).
In addition, salts of the compounds described herein are within the scope of the invention. For example, a salt can be formed between a positively charged amino substituent and a negatively charged counterion.
The details of several embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.
DETAILED DESCRIPTION
The invention features methods for preparing hexasubstituted benzene compounds, the compounds themselves, and EL devices made using these compounds. In particular, the invention features methods for the six-fold substitution of a hexahalobenzene. For example, a hexakis(thienyl)benzene can be synthesized by the palladium-catalyzed thienylation of hexabromobenzene. These starburst-shaped compounds can help improve the physical properties of the organic LEDs into which they are incorporated.
A method for synthesizing a hexaarylbenzene is as follows: If the aryl group is to be substituted, a substituted aryl or heteroaryl comp

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