# US 8,785,671 B2 · 6,13-dihalogen-5,14-dihydropentacene derivative and method for producing 6,13-substituted-5,14-dihydropentacene derivative using same

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- Number: US 8,785,671 B2
- Document ID: US8785671B2
- Status: Granted
- Kind: B2
- Application number: 13/261,420
- Filed: 2011-03-04
- Published: 2013-03-28
- Granted: 2014-07-22
- Earliest claimed: 2010-03-04
- Assignees: National University Corporation Hokkaido University
- Applicants: Tamotsu Takahashi; Ken-ichiro Kanno; Shi Li
- Inventors: Tamotsu Takahashi; Ken-ichiro Kanno; Shi Li
- Web page: https://patentgrep.com/patent/US8785671B2

## CPC

- C07C 13/62: with more than three condensed rings
- C07C 1/26: starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C 1/30: by splitting-off the elements of hydrogen halide from a single molecule
- C07C 25/22: with condensed rings
- C07D 333/08: Hydrogen atoms or radicals containing only hydrogen and carbon atoms
- C07D 333/18: by sulfur atoms
- C07F 15/006: {Palladium compounds}
- C07C 2603/52: containing five condensed rings
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

The present invention provides a 6,13-dihalogen-5,14-dihydropentacene derivative and a method for production thereof. Compounds (b) and (c) are reacted through cross-coupling reaction in the presence of a metal compound and a lithiating agent to synthesize compound (d), which is then halogenated to thereby obtain a 6,13-dihalogen-5,14-dihydropentacene derivative (compound (e)). [wherein X1 and X2 are each a halogen atom, and R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are each a hydrogen atom, an optionally substituted C1-C20 hydrocarbon group, etc.]

## Claims

### Claim 1

A 6,13-dihalogen-5,14-dihydropentacene derivative represented by the following formula (I):
[wherein X1 and X2, which may be the same or different, are each independently a halogen atom, and R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10, which may be the same or different, are each independently a hydrogen atom; an optionally substituted C1-C20 hydrocarbon group; an optionally substituted C1-C20 alkoxy group; an optionally substituted C6-C20 aryloxy group; an optionally substituted C1-C20 alkoxycarbonyl group; an optionally substituted C6-C20 aryloxycarbonyl group; an optionally substituted carbamoyl group; an optionally substituted amino group or an optionally substituted silyl group, wherein if the hydrocarbon group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the amino group or the silyl group has a substituent(s), the substituent(s) is/are selected from the group consisting of a C1-C10 hydrocarbon group, a C1-C10 alkoxy group, a C6-C12 aryloxy group, an amino group, a hydroxyl group, a halogen atom and a silyl group].

### Claim 2 (depends on 1)

The derivative according to claim 1, wherein X1 and X2 are each an iodine atom.

### Claim 3 (depends on 1)

The derivative according to claim 1, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10, which may be the same or different, are each independently a hydrogen atom; an optionally substituted C1-C20 alkyl group; an optionally substituted C6-C20 aryl group or an optionally substituted silyl group.

### Claim 4 (depends on 1)

The derivative according to claim 1, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are each a hydrogen atom.

### Claim 5

A method for producing a 6,13-substituted 5,14-dihydropentacene derivative represented by the following formula (II):
[wherein A1 and A2, which may be the same or different, are each independently an optionally substituted C1-C20 hydrocarbon group; an optionally substituted heteroaryl group; an optionally substituted C1-C20 alkoxy group; an optionally substituted C6-C20 aryloxy group; an optionally substituted C1-C20 alkoxycarbonyl group; an optionally substituted C6-C20 aryloxycarbonyl group; an optionally substituted carbamoyl group; an optionally substituted amino group or an optionally substituted silyl group, wherein if the hydrocarbon group, the heteroaryl group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the amino group or the silyl group has a substituent(s), the substituent(s) is/are selected from the group consisting of a C1-C10 hydrocarbon group, a C1-C10 alkoxy group, a C6-C12 aryloxy group, an amino group, a hydroxyl group, a halogen atom and a silyl group, and
R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10, which may be the same or different, are each independently a hydrogen atom; an optionally substituted C1-C20 hydrocarbon group; an optionally substituted C1-C20 alkoxy group; an optionally substituted C6-C20 aryloxy group; an optionally substituted C1-C20 alkoxycarbonyl group; an optionally substituted C6-C20 aryloxycarbonyl group; an optionally substituted carbamoyl group; an optionally substituted amino group or an optionally substituted silyl group, wherein if the hydrocarbon group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the amino group or the silyl group has a substituent(s), the substituent(s) is/are selected from the group consisting of a C1-C10 hydrocarbon group, a C1-C10 alkoxy group, a C6-C12 aryloxy group, an amino group, a hydroxyl group, a halogen atom and a silyl group],
said method comprising the step of reacting a 6,13-dihalogen-5,14-dihydropentacene derivative represented by the following formula (I):
[wherein X1 and X2, which may be the same or different, are each independently a halogen atom, and R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are the same as defined in formula (II)] with an organometallic compound comprising A1 or A2 as defined in formula (II) in the presence of a transition metal catalyst.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the organometallic compound is selected from the group consisting of an organolithium compound, an organomagnesium compound, an organoaluminum compound, an organozinc compound, an organoboron compound and an organosilyl compound.

### Claim 7 (depends on 5)

The method according to claim 5, wherein the organometallic compound is any of compounds represented by formulae (1) to (6):
RLi (1)
RmgY (2)
R3Al (3)
RznY (4)
RBY2 (5)
RSiR′3 (6)
[wherein each R, which may be the same or different, is independently A1 or A2 as defined in formula (II), each Y, which may be the same or different, is independently a halogen atom or a hydroxy group, and R′ is a C1-C10 alkyl group].

### Claim 8 (depends on 5)

The method according to claim 5, wherein the transition metal catalyst comprises a nickel complex or a palladium complex.

### Claim 9 (depends on 5)

The method according to claim 5, wherein A1 and A2, which may be the same or different, are each independently an optionally substituted C1-C20 alkyl group, an optionally substituted C2-C20 alkenyl group, an optionally substituted C2-C20 alkynyl group, an optionally substituted C6-C20 aryl group or an optionally substituted heteroaryl group.

### Claim 10 (depends on 5)

The method according to claim 5, wherein X1 and X2 are each an iodine atom.

### Claim 11 (depends on 5)

The method according to claim 5, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10, which may be the same or different, are each independently a hydrogen atom; an optionally substituted C1-C20 alkyl group; an optionally substituted C6-C20 aryl group or an optionally substituted silyl group.

### Claim 12 (depends on 5)

The method according to claim 5, wherein R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are each a hydrogen atom.

### Claim 13

A complex compound represented by the following formula (IV):
[wherein X1 and X2, which may be the same or different, are each independently a halogen atom, R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10, which may be the same or different, are each independently a hydrogen atom; an optionally substituted C1-C20 hydrocarbon group; an optionally substituted C1-C20 alkoxy group; an optionally substituted C6-C20 aryloxy group; an optionally substituted C1-C20 alkoxycarbonyl group; an optionally substituted C6-C20 aryloxycarbonyl group; an optionally substituted carbamoyl group; an optionally substituted amino group or an optionally substituted silyl group, wherein if the hydrocarbon group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the amino group or the silyl group has a substituent(s), the substituent(s) is/are selected from the group consisting of a C1-C10 hydrocarbon group, a C1-C10 alkoxy group, a C6-C12 aryloxy group, an amino group, a hydroxyl group, a halogen atom and a silyl group, and Ra and Rb, which may be the same or different, are each independently an optionally substituted C1-C20 alkyl group or an optionally substituted C6-C20 aryl group].

### Claim 14

A method for producing a 6,13-substituted 5,14-dihydropentacene derivative represented by the following formula (II):
[wherein A1 and A2, which may be the same or different, are each independently an optionally substituted C1-C20 hydrocarbon group; an optionally substituted heteroaryl group; an optionally substituted C1-C20 alkoxy group; an optionally substituted C6-C20 aryloxy group; an optionally substituted C1-C20 alkoxycarbonyl group; an optionally substituted C6-C20 aryloxycarbonyl group; an optionally substituted carbamoyl group; an optionally substituted amino group or an optionally substituted silyl group, wherein if the hydrocarbon group, the heteroaryl group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the amino group or the silyl group has a substituent(s), the substituent(s) is/are selected from the group consisting of a C1-C10 hydrocarbon group, a C1-C10 alkoxy group, a C6-C12 aryloxy group, an amino group, a hydroxyl group, a halogen atom and a silyl group, and
R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10, which may be the same or different, are each independently a hydrogen atom; an optionally substituted C1-C20 hydrocarbon group; an optionally substituted C1-C20 alkoxy group; an optionally substituted C6-C20 aryloxy group; an optionally substituted C1-C20 alkoxycarbonyl group; an optionally substituted C6-C20 aryloxycarbonyl group; an optionally substituted carbamoyl group; an optionally substituted amino group or an optionally substituted silyl group, wherein if the hydrocarbon group, the alkoxy group, the aryloxy group, the alkoxycarbonyl group, the aryloxycarbonyl group, the carbamoyl group, the amino group or the silyl group has a substituent(s), the substituent(s) is/are selected from the group consisting of a C1-C10 hydrocarbon group, a C1-C10 alkoxy group, a C6-C12 aryloxy group, an amino group, a hydroxyl group, a halogen atom and a silyl group],
said method comprising the step of reacting a complex compound represented by the following formula (IV):
[wherein X1 and X2, which may be the same or different, are each independently a halogen atom, R1, R2, R3, R4, R5, R6, R7, R8, R9 and R10 are the same as defined in formula (II), and Ra and Rb, which may be the same or different, are each independently an optionally substituted C1-C20 alkyl group or an optionally substituted C6-C20 aryl group] with an organometallic compound comprising A1 or A2 as defined in formula (II).