Method for synthesis of nitroxyl radical
AssigneeKyushu University, National University Corporation
InventorsHideo Utsumi, Kiyoshi Sakai, Kenichi Yamada
Life of this patent
Estimating the term…
Abstract
The problem to be solved by the present invention is to provide a highly-versatile method for producing a nitroxyl radical derivative, in which position-2 and position-6 in a TEMPO-based compound can be easily substituted, and further, a method for producing a nitroxyl radical derivative, in which a nitrogen nucleus is labeled with 15N. The above-described problem can be solved by reacting a triacetoneamine derivative with ketone or aldehyde in the presence of ammonium salt or a 15N-labeled compound thereof to obtain a 2,6-substituted-4-piperidone derivative.
Claims15
A method for producing a 2,6-substituted-4-piperidone derivative represented by the following formula:
- wherein in the formula:
- R1, R2, R3 and R4 are each independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C4-C20 alkyldienyl group, a C6-C18 aryl group, a C6-C20 alkylaryl group, a C6-C20 arylalkyl group, a C4-C20 cycloalkyl group, a C4-C20 cycloalkenyl group, or a (C3-C10 cycloalkyl) C1-C10 alkyl group, and the aforementioned groups may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom;
- any one of R1, R2, R3 and R4 is a group other than a hydrogen atom;
- and R1 and R2 and/or R3 and R4 may be independently crosslinked to each other to form a substituted or unsubstituted C4-C40 monocyclic or polycyclic saturated ring, and the saturated ring may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom,
- wherein the method comprises the step of reacting a triacetoneamine derivative represented by formula (1):
- wherein in the formula:
- R is a hydrogen atom or a C1-C6 alkyl group;
- and the R′ groups are each independently a C1-C6 alkyl group,
- with the proviso that when the triacetoneamine derivative represented by the formula (1) is completely identical to the 2,6-substituted-4-piperidone derivative represented by the formula (1), it is excluded, with a ketone or aldehyde derivative represented by formula (2):
- wherein in the formula:
- R5 and R6 are each independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C4-C20 alkyldienyl group, a C6-C18 aryl group, a C6-C20 alkylaryl group, a C6-C20 arylalkyl group, a C4-C20 cycloalkyl group, a C4-C20 cycloalkenyl group, or a (C3-C10 cycloalkyl) C1-C10 alkyl group, and the aforementioned groups may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom;
- any one of R5 and R6 is a group other than a hydrogen atom;
- and R5 and R6 may be crosslinked to each other to form a substituted or unsubstituted C4-C40 monocyclic or polycyclic saturated ring, and the saturated ring may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom, in the presence of ammonium salt.
A 2,6-substituted-4-piperidone derivative represented by formula (1′):
- wherein in the formula:
- R1′, R2′, R3′ and R4′ are each independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C4-C20 alkyldienyl group, a C6-C18 aryl group, a C6-C20 alkylaryl group, a C6-C20 arylalkyl group, a C4-C20 cycloalkyl group, a C4-C20 cycloalkenyl group, or a (C3-C10 cycloalkyl) C1-C10 alkyl group, and the aforementioned groups may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom;
- any one of R1′, R2′, R3′ and R4′ is a group other than a hydrogen atom;
- and R1′ and R2′ and/or R3′ and R4′ are independently crosslinked to each other to form a substituted or unsubstituted C4-C40 monocyclic or polycyclic saturated ring, and the saturated ring may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom, with the proviso that R1′ and R2′ and/or R3′ and R4′ do not form a cyclohexane ring with no substituent.
A 2,6-substituted-4-piperidone derivative represented by:
A nitroxyl radical derivative represented by formula (II′):
- wherein in the formula:
- R1′, R2′, R3′ and R4′ are each independently a hydrogen atom, a C1-C20 alkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, a C4-C20 alkyldienyl group, a C6-C18 aryl group, a C6-C20 alkylaryl group, a C6-C20 arylalkyl group, a C4-C20 cycloalkyl group, a C4-C20 cycloalkenyl group, or a (C3-C10 cycloalkyl) C1-C10 alkyl group, and the aforementioned groups may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom;
- any one of R1′, R2′, R3′ and R4′ is a group other than a hydrogen atom;
- and R1′ and R2′ and/or R3′ and R4′ are independently crosslinked to each other to form a substituted or unsubstituted C4-C40 monocyclic or polycyclic saturated ring, and the saturated ring may be interrupted by an oxygen atom, a nitrogen atom or a sulfur atom, with the proviso that R1′ and R2′ and/or R3′ and R4′ do not form a cyclohexane ring with no substituent.
A nitroxyl radical derivative represented by:
Dependencies are inferred from the claim text.