15258-52-3Relevant academic research and scientific papers
AMINO-CLAISEN REARRANGEMENT. II. QUATERNARY AMINO-CLAISEN REARRANGEMENT OF ANILINIUM COMPOUNDS WITH ORTHO SUBSTITUENTS
Katayama, Hajime,Takatsu, Noriyuki
, p. 2465 - 2477 (2007/10/02)
Amino(N)-Claisen rearrangement of quaternary aniline derivatives with ortho substituents was investigated in relation to that of corresponding tertiary anilines.N-allylated anilinium compounds 1 with a freely rotating ortho substituent such as a methyl or methoxy group yielded mostly the deallylated products 4 along with minor amounts of rearrangement products 2 and 3.The corresponding tertiary anilines yielded ortho rearrangement products 6 together with para ones 7.The quaternary N-Claisen rearrangement of N-allylated 1,2,3,4-tetrahydroquinolinium salts 14 and indolinium salts 22 in which the ortho substituents are locked in rings afforded the ortho rearrangement products 15 and 23, respectively in good yields.N-Claisen rearrangement of the corresponding aromatic tertiary amines 18 also took place in good yield.The above rearrangements could be rationalized on the basis of mechanistic considerations.Keywords: - quaternary amino-Claisen rearrangement; mechanism; sigmatropic rearrangement; N-allyl-N,N-dimethyl-o-toluidinium bromide; N-allyl-N,N-dimethyl-o-anisidinium bromide; 1-allyl-1-methyl-1,2,3,4-tetrahydroquinolinium halides; 1-allyl-1,2-dimethylindolinium bromide; 8-allyl-1-methyl-1,2,3,4-tetrahydroquinoline; 6-allyl-1-methyl-1,2,3,4-tetrahydroquinoline; 7-allyl-1,2-dimethylindoline
