Indanone oximes

Quinolin-2-one, 3-cyano-4-hydroxy-synthesis, 2, 428 Quinolin-2-one, 3,4-dialkyl-Knorr synthesis, 2, 425 Quinolin-2-one, dihydro-Camps synthesis, 2, 418 synthesis, 2, 402 from benzazepinones, 2, 506 from indanone oxime, 2, 487 from indanones, 2, 488 by intramolecular Friedel-Crafts reactions, 2, 421... 

Lee and coworkers ", studying the Beckmann rearrangement of 1-indanone oxime derivatives 240, observed that the pure E and Z oximes isomerize under mild acidic conditions such as silica gel (equation 72). In the presence of Brpnsted or Lewis acids as silica gel or AICI3 the high rotational barrier of C=N double bond would be lowered by the formation of a complex between the tosylate and AICI3 241. This fact makes the... 

The Beckmann rearrangement of oxime esters is catalysed by Brpnsted or Lewis acids and these conversions are usually non-stereospecific, as demonstrated by the studies of Beckmann rearrangement of 1-indanone oximes derivatives 240a with aluminium chloride as a catalyst " (equation 88). 

The stereoselectivity of the acidic rearrangement of indanone oximes 378 into the carbostyril core was found to be dependent on the substiments of the aromatic ring (equation 150). Moderate yields were observed. 

The oxime nitrogen lone pair of electrons must be properly oriented so as to interact with the rhodium carbenoid.84 Thus, subjection of the -oximino isomer 182 to a catalytic quantity of Rh2(OAc)4 in CH2C12 (40 °C) with a slight excess of DMAD afforded the bimolecular cycloadduct 184 in 93% yield. In sharp contrast, when the isomeric Z-oximino diazo derivative 183 was exposed to the same reaction conditions, only indanone-oxime 185 (80%) was obtained. The formation of this product is most likely the result of an intramolecular C-H insertion reaction. 

The presence of ammonia may depress the formation of a secondary amine, and quite high yields of primary amines have often been obtained with ketoximes over Raney Ni in the presence of ammonia, as seen in the hydrogenation of l-(4-ethoxy-3-methoxyphenyl)-2-propanone oxime (eq. 8.15)24 and 3,3-dimethyl-l-indanone oxime,25 where the corresponding primary amine was obtained in 95 and 92% yields, respectively. 

Rosen and Green obtained high yields (90-95%) of 2-aminoindane hydrochloride by hydrogenation of 2-indanone oxime over a commercial 5% Pd-C in acetic acid-sulfiiric... 

Scheme 8.4 Products of hydrogenation of 2-indanone oxime over 5% Pt-C in various solvents (room temperature 0.31-0.28 MPaH2).

The indanone oximes (7) gave the aryl- and alkyl-migrated products (8) and (9) (equation 6), with the proportion of (9) itKteasing with increasing steric demand of arenc substituents at the 4- and 7-positions. Exposure of the ( )-oxime (10) to phosphorus pentoxide and methanesulfonic acid gave the product (11) of migration of the yn-alkyl group, presumably via the (Z)-isomer (equation 7). 

A mixture of 4-bromo-7-ferf-butyl-l-indanone oxime and polyphosphoric acid heated to 130°, kept 1 min. at this temp., allowed to cool to room temp., and the product isolated as the perchlorate l,8-ethano-7-bromo-4,4-dimethyl-3,4-dihydroisoquinoline perchlorate. Y 70-75%. P. T. Lansbury, J. G. Colson, and N. R. Mancuso, Am. Soc. 86, 5225 (1964). 

Related chemistry was reported by Saeki and Toyota for the racemic S5mthesis of natural product CIS-195A (64), an alkaloid that has been isolated from dendrobatid frog skin extracts tScheme A 1 1 mixture of indanone oxime stereoisomers 62 underwent a... 

Mixtures of polyphosphoric acid (PPA) or K-10 clay and Bi(OTf)3 xH20 have been reported to be efficient systems for the rearrangement of indanone oximes (Equation 36) [73]. The apparent synergy between PPA and Bi(OTf)3 xH20 might be rationalized as Bronsted acid assisted Lewis acid (BLA) catalysis. 

A soln. of 2-indanone oxime in methanol previously satd. with HGl-gas stirred and refluxed 8 hrs. under anhydrous conditions 2-amino-1-indanone hydrochloride. Y 45.7%. Limitations s. W. E. Rosen and M. J. Green, J. Org. Ghem. 28,2197 (1963). 

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