Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-11-08
2002-07-09
Davis, Brian J. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C558S252000, C558S256000, C560S038000, C560S039000, C560S040000, C560S042000
Reexamination Certificate
active
06417368
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a resin-immobilized amine derivative and a solid state synthesis method of &bgr;-aminocarbonyl compound.
2. Description of the Related Art
For peptide synthesis, for example, solid state synthesis methods using resin carriers have been known conventionally. Such solid state synthesis methods are effective means for simultaneous synthesis of a group of numerous types of analogous compounds. It has been suggested that solid state synthesis methods are applicable to various chemical reactions.
Practically, however, reactions to which solid state reaction is applicable are limited, disadvantageously, compared with liquid phase reaction as the principal reaction for chemical synthesis.
In such circumstances of the related art concerning solid state synthesis methods, the inventors of the present application have investigated about the enhancement of the effectiveness of solid state synthesis methods by efficiently progressing the most essential and important reaction for generating carbon—carbon bond in organic synthesis in solid phase.
The inventors of the application have found a new method for iminoaldol-type addition reaction with a catalyst, using as the starting material an imine compound recovered from the reaction of an amine compound with aldehydes. Therefore, it has increasingly been an important problem to establish a solid state synthesis method capable of practically more enhancing the efficiency of the method.
It is therefore a purpose of the invention of the application to provide new technical means for realizing the iminoaldol-type addition reaction as described above by a solid state synthesis method; more specifically, it is a purpose of the invention to provide a method for synthesizing &bgr;-aminocarbonyl compounds, comprising applying a solid state synthesis reaction.
SUMMARY OF THE INVENTION
So as to attain the foregoing objectives, the present application provides a resin-immobilized &bgr;-aminocarbonyl compound represented by the following formula in a first aspect of the invention:
wherein P represents the principal chain of a resin polymer; Q represents a substituted or unsubstituted hydrocarbon side chain or a substituted or unsubstituted hydrocarbon side chain with a heteroatom interposed therein; R, and R
2
and R
3
independently represent a substituted or unsubstituted hydrocarbon group or heterocyclic group; R
1
represents —OR
0
, —SR
0
or R
0
(R
0
represents a substituted or unsubstituted hydrocarbon group or heterocyclic group).
In a second aspect of the invention, the application provides a resin-immobilized &bgr;-aminocarbonyl compound of the aforementioned formula where, the hydrocarbon side chain Q represents the following formula:
—Q
1
—O—Q
2
— (in formula, Q
1
and Q
2
independently represent a substituted or unsubstituted hydrocarbon chain such as arylene, alkylenearylene or arylenealkylene).
The application provides a method for producing a resin-immobilized &bgr;-aminocarbonyl compound in a third aspect of the invention, comprising allowing a resin immobilized imine of the formula I: P—Q—N═CH—R to react with a silyl ether.
In a fourth aspect of the invention, the application provides a method for producting &bgr;-aminocarbonyl compound represented by either one of the following formulas (A)
(where Q
0
represents a substituent which is the remaining part of the side chain Q after the &bgr;-aminocarbonyl compound is separated from the resin) or (B)
comprising the cleavage of the &bgr;-aminocarbonyl from the resin of the resin-immobilized &bgr;-aminocarbonyl compound.
In a fifth aspect of the invention, the application provides a method for producing a &bgr;-aminocarbonyl compound, comprising treatment of the resin-immobilized &bgr;-aminocarbonyl compound of above formula II with a Lewis acid.
DETAILED DESCRIPTION OF THE INVENTION
The application provides a resin-immobilized &bgr;-aminocarbonyl compound represented by the formula II according to the first and second aspects of the invention. These have never been know to enable the solid state synthesis method of &bgr;-aminocarbonyl compounds.
In the resin-immobilized &bgr;-aminocarbonyl compound of the formula II, as described above, P represents the principal chain of a resin polymer and Q represents a side chain to bind to the principal chain, wherein the resin polymer composing the principal chain includes any of addition polymers, condensed polymers and cross-linked polymers thereof but preferably includes addition polymers of alkenes with carbon—carbon double bond or cross-linked polymers thereof. The alkenes include aliphatic olefins and aliphatic dienes and also include, &agr;, &bgr;-aliphatic unsaturated carboxylic acids or esters thereof, &agr;, &bgr;-aliphatic unsaturated nitriles and aromatic alkenes such as styrene, &agr;-methylstyrene and divinylbenzene. The addition polymers thereof or partially cross-linked polymers thereof are preferable.
It is needless to say that various condensed polymers of polyester, epoxy resins, polyether and polyamide are also included.
In accordance with the invention, the side chain Q includes substituted or unsubstituted hydrocaron chains or substituted or unsubstituted hydrocarbon chains with heteroatoms such as oxygen atom or nitrogen atom interposed therein, wherein the hydrocarbon chains then include various hydrocarbon chains such as aliphatic, alicyclic, aromatic and aromatic aliphatic hydrocarbon chains and are for example alkylene chain represented by —(CH
2
)
n
— and phenylenealkylene chain. Otherwise, the hydrocarbon chains can satisfactorily be hydrocarbon chains with heteroatoms interposed therein.
These side chains Q are satisfactorily formed together with the principal chain P and are also satisfactorily formed by graft polymerization after the principal chain P is formed.
As the side chain Q, for example, hydrocarbon chains derived from the resin-immobilized amine P—Q
1
—O—Q
2
—NH
2
are provided in accordance with the invention, wherein Q
1
and Q
2
are arylene, alkylenearylene or arylenealkylene. Specifically, preferable examples of the hydrocarbon chains are hydrocarbon chains with Ph (pheylene chain), such as —Ph—, —(CH
2
)
n
—Ph, —PH—(CH
2
)
n
—, —Ph—(CH
2
)
n
—Ph—, particularly oxyphenylene chains, such as —Ph—O—Ph—, —Ph—(CH
2
)
n
—O—Ph—, —Ph—(CH
2
)
n
—O—(CH
2
)
n
—Ph.
These hydrocarbons can satisfactorily have various substituents with no inhibition of the solid state synthesis reaction but with an activity to activate the reaction. The substituents include hydrocarbon groups such as alkyl group and aryl group, halogen atom, alkoxyl group, acyloxy group, alkoxycarbonyl group, nitro group, cyano group and heterocyclic group.
R, R
2
and R
3
, and R
0
composing R
1
in the resin-immobilized &bgr;-aminocarbonyl group of the formula II represent substituted or unsubstituted hydrocarbon groups or heterocyclic groups, wherein the hydrocabon groups include various linear or cyclic aliphatic or aromatic or aromatic aliphatic hydrocarbon groups, saturated or unsaturated. Similary, the heterocyclic groups include various heterocyclic groups containing oxygen or nitrogen. These are satisfactorily substituted with various substituents with no inhibition of the solid state synthesis reaction but with an activity to activate the reaction, for example hydrocarbon groups such as alkyl group and aryl group, halogen atom, alkoxyl group, acyloxy group, alkoxycarbonyl group, nitro group, cyano group and heterocyclic group.
In accordance with the invention, further, the resin-immoiblized amine of the formula III P—Q
1
—O—Q
2
—NH
2
is provided as a substrate for the solid state synthesis of compounds containing nitrogen such as amino group. The resin-immobilized amine is essentially required for constructing a library of nitrogen-containing compounds for the solid state synthesis.
For example, —Q
1
—O—Q
2
— is more specifically described as such a structure as —Ph—CH
2
—O—Ph—CH
2
—.
The reaction of various resin-immobilized amines including th
Aoki Yoji
Kobayashi Shu
Davis Brian J.
Japan Science and Technology Corporation
Wenderoth Lind & Ponack LLP
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