Organic compounds -- part of the class 532-570 series – Organic compounds – Nitrogen attached directly or indirectly to the purine ring...
Reexamination Certificate
2000-03-10
2002-02-12
Raymond, Richard L. (Department: 1624)
Organic compounds -- part of the class 532-570 series
Organic compounds
Nitrogen attached directly or indirectly to the purine ring...
C546S135000, C546S277100, C548S336500, C548S452000, C548S467000
Reexamination Certificate
active
06346621
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to nitrogen-heterocyclic compounds (nitrogen-containing heterocyclic compounds), and a process for producing the compound. More specifically, the present invention relates to nitrogen-heterocyclic compounds substituted at 1-position by an amino group, including 1-aminoindole derivatives and 1-amino-4H quinoline derivatives, and intermediates therefore.
The present invention relates also to a process for producing a nitrogen-heterocyclic compound including indole derivatives and 4H-quinoline derivatives, the process comprising cyclizing intramolecularly a hydrazone derivative having a halogenated aryl group in the presence of a catalyst composed of a phosphine and a palladium compound.
The present invention relates further to a process for producing a substituted indole derivative, comprising cyclizing intramolecularly a hydrazone derivative having a halogenated aryl group in the presence of a catalyst composed of a phosphine and a palladium compound, an amine, and a base, and introducing simultaneously an amino group to the non-nitrogen aromatic ring (aromatic ring not containing nitrogen).
These nitrogen-heterocyclic compounds are useful as a source material for medicines and pesticides, and for electronic materials.
2. Description of the Related Art
Nitrogen-heterocyclic compounds substituted at 1-position by an amino group are disclosed: 1-(pyridylamino)-indoles are disclosed as an anancastic disease remedy in JP-A-7-53376 (the term “JP-A” herein means an “unexamined published Japanese patent application”), and 1-(phenylamino)indoles are disclosed in JP-A-60-142955.
On the other hand, many processes are investigated for the synthesis of nitrogen-heterocyclic compound. In particular, for indole derivatives, various processes are well known such as a Fischer process, a Reissert process, and a Bischler process. In recent years, new processes have been disclosed: a process starting from a nitrostyrene catalyzed by use of palladium-copper-oxygen disclosed in JP-A-3-24055; synthesis of an indole derivative by preparing an indoline compound in the presence of palladium/phosphine catalyst and dehydrogenating it in the presence of palladium carbon (S. L. Buchwald et al.: J. Am. Chem. Soc. 1998, Vol. 120, pp. 3068-3073); indole synthesis by catalytic cyclization of o-iodoaniline with a ketone in the presence of a palladium catalyst (C. Chen et al.: J. Org. Chem., 1997, Vol. 62, pp. 2676-2677); indole synthesis by catalytic cyclization of o-iodoaniline with an alkyne in the presence of a palladium catalyst (R. C. Larock et al: J. Org. Chem., 1998, Vol. 63, pp. 7652-7662); and indole synthesis by reductive cyclization employing an o-nitrotoluene derivative (A. D. Batcho et al.: Organic Syntheses, 1985, Vol. 63, pp.214-224).
A process for synthesis of 1-aminoindole is reported in which o-nitrosophenylethylamine is electrochemically converted (B. A. F. Uribe et al.: European Journal of Organic Chemistry, 1999, Vol.2, pp.419-430).
The arylpiperazine structure is important in remedy for brain malfunction such as an antidepressant. For example, arylpiperazines are useful for remedy for brain malfunction such as an antidepressant, and importance of this structure for pharmacological activity are described by R. A. Glennon et al.: Drug Development Research, 22 (1993), pp.25-36; R. M. Pindler et al.: Medicinal Research Reviews, 13 (1993), pp.259-325, and R. A. Glennon et al.: Journal of Medicinal Chemistry, 32 (1989), pp.1921-1926.
Diarylamines are described to be useful as the intermediates for medicines and pesticides and for electronic intermediate material in Yuki Gosei Kyokai-Shi (Journal of the Organic Synthesis Society, Japan), Vol.52 (1994) pp.1083-1088. Triarylamines having high electron carrying ability are described to be useful as a hole carrier in organic electroluminescence by Seizo MIYATA (“Organic EL Elements and Industrial Front Thereof”, pp.22-27, pp.104-106, NTS Co.).
As shown above, the diarylamine or triarylamine structure having a longer conjugation system is superior to the monoarylamine structure in the properties and functions in the aforementioned application fields. The structure of diarylamine, triarylamine, or N-arylazole is essential to the electronic materials such as the hole carrier in organic electroluminescence.
However, in the aforementioned known nitrogen-heterocyclic compounds (namely, indole derivatives having an amino group at 1-position), the kinds of the substituents on the non-nitrogen aromatic ring are limited, and the position of the substitution is limited to 3- and 5-positions of the indole. The nitrogen-heterocyclic compound is not known which has an amino group at 1-position and has a non-nitrogen aromatic ring substituted by a 1-piperazinyl, arylamino, diarylamino, or azolyl group (the azolyl group including cyclic amino groups such as pyrrolyl and indolyl).
In the conventional production processes mentioned above, the source materials cannot readily be available, and in synthesis of substituted indole, the position of the substituent on the indole ring is limited mainly to 5-, 6-, or 7-position. For example, an indole derivative having a substituent at 4-position only cannot readily be synthesized by the conventional process.
The present invention has been made to solve the above problems of the prior art.
SUMMARY OF THE INVENTION
The present invention intend to provide a heterocyclic compound having, on the non-nitrogen aromatic ring, a substituent such as 1-piperazinyl, arylamino-, diarylamino, azolyl, alkoxy, and nitro.
The present invention intends also to provide a nitrogen-heterocyclic compound having a halogen atom on the aromatic ring useful as the source material of the above substituted nitrogen-heterocyclic compound.
The present invention intends further to provide a process for synthesizing, in a simple manner, the nitrogen-heterocyclic compound such as indole derivatives and 4H-quinoline derivatives useful as a source material for medicines, pesticides, and electronic materials from readily available source materials.
After comprehensive investigation to solve the above problems, the inventors of the present invention have found the nitrogen-heterocyclic compound of the present invention, and the process for production thereof. Thus the present invention has been completed.
In an aspect of the present invention, there is provided a nitrogen-heterocyclic compound represented by General Formula (1) below:
where R
1
and R
2
are independently hydrogen, an alkyl group, an aryl group, or a heteroaryl group; R
3
is hydrogen or an aryl group; R
4
is a substituted amino group, an alkoxy group, a nitro group, or halogen; m is an integer from 0 to 2; and n is 0 or 1. A process for producing the above compound is also provided.
In another aspect of the present invention, there is provided a nitrogen-heterocyclic compound represented by General Formula (2) below:
where R
1
and R
2
are independently hydrogen, an alkyl group, a phenyl group, a substituted phenyl group, a furyl group, or a thienyl group; R
3
is hydrogen or an aryl group; R
4
is a substituted amino group; m is 1 or 2; and n is 0 or 1. An intermediate thereof, and a process for producing the above compound are also provided.
In a further aspect of the present invention, there is provided a process for producing a substituted indole derivative represented by General Formula (7) below:
where R
1
and R
2
are independently hydrogen, an alkyl group, an aryl group, or a heteroaryl group; R
3
is hydrogen or an aryl group; R
5
and R
6
are independently hydrogen, an alkyl group, or an aryl group, and R
5
and R
6
may be linked suitably to form a hetero-ring.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is described below in detail.
1. Nitrogen-Heterocyclic Compound Represented by General Formula (1):
In this embodiment of the present invention, the compound represented by General Formula (1) is produced by intramolecular cyclization of a hydrazone compound represe
Nishiyama Masakazu
Watanabe Makoto
Yamamoto Toshihide
Balasubramanian Venkalaraman
Tosoh Corporation
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