9-azanoradamantane n-oxyl compound and method for producing same, and organic oxidation catalyst and method for oxidizing alcohols using 9-azanoradamantane n-oxyl compound

A method for producing the 9-azanoradamantane N-oxyl compound represented by the formula (1),

• the method producing the 9-azanoradamantane N-oxyl compound through at least a step of closing the ring of a hydrazonoazabicyclo[3.3.1]nonane compound of the formula (3) below and forming an azanoradamantane ring, and oxidizing the resulting azanoradamantane compound represented by the formula (2):
• wherein R1 and R2 have the same definitions as described above;
• R3 represents at least one substituent selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a mercapto group, an amino group, a formyl group, a carboxyl group, a sulfo group, a linear or branched C1-12 alkyl group, a C3-12 cycloalkyl group, a (C1-12 alkyl)oxy group, a (C3-12 cycloalkyl)oxy group, a (C1-12 alkyl)thio group, a (C3-12 cycloalkyl)thio group, a (C1-12 alkyl)amino group, a (C3-12 cycloalkyl)amino group, a di(C1-6 alkylamino group, a di(C3-6 cycloalkyl)amino group, a C1-12 alkylcarbonyl group, a C3-12 cycloalkylcarbonyl group, a (C1-12 alkyl)oxycarbonyl group, a (C3-12 cycloalkyl)oxycarbonyl group, a (C1-12 alkyl)thiocarbonyl group, a (C3-12 cycloalkyl)thiocarbonyl group, a (C1-12 alkyl)aminocarbonyl group, a (C3-12 cycloalkyl)aminocarbonyl group, a di(C1-6 alkyl)aminocarbonyl group, a di(C3-6 cycloalkyl)aminocarbonyl group, a (C1-12 alkyl)carbonyloxy group, a (C3-12 cycloalkyl)carbonyloxy group, a (C1-12 alkyl)carbonylthio group, a (C3-12 cycloalkyl)carbonylthio group, a (C1-12 alkyl)carbonylamino group, a (C3-12 cycloalkyl)carbonylamino group, a di(C1-12 alkylcarbonyl)amino group, a di(C3-12 cycloalkylcarbonyl)amino group, a C1-6 haloalkyl group, a C3-6 halocycloalkyl group, a C2-6 alkenyl group, a C3-6 cycloalkenyl group, a C2-6 haloalkenyl group, a C3-6 halocycloalkenyl group, a C2-6 alkynyl group, a C2-6 haloalkynyl group, a benzyl group which may be optionally substituted with Ra, a benzyloxy group which may be optionally substituted with Ra, a benzylthio group which may be optionally substituted with Ra, a benzylamino group which may be optionally substituted with Ra, a dibenzylamino group which may be optionally substituted with Ra, a benzylcarbonyl group which may be optionally substituted with Ra, a benzyloxycarbonyl group which may be optionally substituted with Ra, a benzylthiocarbonyl group which may be optionally substituted with Ra, a benzylaminocarbonyl group which may be optionally substituted with Ra, a dibenzylaminocarbonyl group which may be optionally substituted with Ra, a benzylcarbonyloxy group which may be optionally substituted with Ra, a benzylcarbonylthio group which may be optionally substituted with Ra, a benzylcarbonylamino group which may be optionally substituted with Ra, a di(benzylcarbonyl)amino group which may be optionally substituted with Ra, an aryl group which may be optionally substituted with Ra, an aryloxy group which may be optionally substituted with Ra, an arylthio group which may be optionally substituted with Ra, an arylamino group which may be optionally substituted with Ra, a diarylamino group which may be optionally substituted with Ra, an arylcarbonyl group which may be optionally substituted with Ra, an aryloxycarbonyl group which may be optionally substituted with Ra, an arylthiocarbonyl group which may be optionally substituted with Ra, an arylaminocarbonyl group which may be optionally substituted with Ra, a diarylaminocarbonyl group which may be optionally substituted with Ra, an arylcarbonyloxy group which may be optionally substituted with Ra, an arylcarbonylthio group which may be optionally substituted with Ra, an arylcarbonylamino group which may be optionally substituted with Ra, and a di(arylcarbonyl)amino group which may be optionally substituted with Ra, wherein the substituents may be the same or different when two or more substituents exist;
• Ra represents halogen, a C1-6 alkyl group, a C1-6 haloalkyl group, a C3-6 cycloalkyl group, a C1-6 alkoxy group, a C1-6 alkoxy C1-6 alkyl group, a C1-6 alkyl sulfenyl C1-6 alkyl group, a C1-6 haloalkoxy group, a C1-6 alkyl sulfenyl group, a C1-6 alkylsulfinyl group, a C1-6 alkylsulfonyl group, a C1-6 haloalkylsulfenyl group, a C1-6 haloalkylsulfinyl group, a C1-6 haloalkylsulfonyl group, a C2-6 alkenyl group, a C2-6 haloalkenyl group, a C2-6 alkenyloxy group, a C2-6 haloalkynyloxy group, a C2-6 alkenylsulfenyl group, a C2-6 alkenylsulfinyl group, a C2-6 alkenylsulfonyl group, a C2-6 haloalkenylsulfenyl group, a C2-6 haloalkenylsulfinyl group, a C2-6 haloalkenylsulfonyl group, a C2-6 alkynyl group, a C2-6 haloalkynyl group, a C2-6 alkynyloxy group, a C2-6 haloalkynyloxy group, a C2-6 alkynyl sulfenyl group, a C2-6 alkynylsulfinyl group, a C2-6 alkynylsulfonyl group, a C2-6 haloalkynyl sulfenyl group, a C2-6 haloalkynylsulfinyl group, a C2-6 haloalkynylsulfonyl group, —NO2, —CN, a formyl group, —OH, —SH, —NH2, —SCN, a C1-6 alkoxycarbonyl group, a C1-6 alkylcarbonyl group, a C1-6 haloalkylcarbonyl group, a C1-6 alkylcarbonyloxy group, a phenyl group, a C1-6 alkylamino group, or a di C1-6 alkylamino group, wherein Ra is substituted in numbers of 1 to 5, and may be the same or different when two or more Ra exist;
• and X represents a hydrogen atom, or a group selected from an acyl group, a carbamoyl group, a sulfoneamide group, an alkyl group, an allyl group, a benzyl group, an aryl group, a silyl group, a hydroxyl group, an alkoxy group, and an oxygen atom.

A method for producing the azanoradamantane N-oxyl compound represented by the formula (1),

• the method comprising:
• synthesizing a ketobicycloamine product through condensation of 2,6-heptanedione, ammonium chloride, and acetonedicarboxylic acid, the 2,6-heptanedione being obtained by methylating a Weinreb diamide produced from glutaryl chloride;
• producing a hydrazone through condensation of the ketobicycloamine product with hydrazine;
• forming an azanoradamantane skeleton under basic condition;
• and
• oxidizing the amino group.