767. Oxindoles formerly regarded as ψ-indoxyls

Abstract

Oxindoles formerly regarded as +Indoxyls. 3475767. Oxindoles formerly regarded as #-Indoxyls.By R. F. MOORE and S. G . P. PLANT.cycloPentanespirooxindole, cyclohexanespirooxindole, and several derivatives of the latter have been synthesised from the appropriate phenylhydrazides of cyclopentane-or cyclohexane-carboxylic acid. Some of these products had hitherto been regarded as +indoxyls. The position of the substituent in the nitration product of cyclohexanespirooxindole has been established, and the course of the Friedel-Crafts reaction in the 3 : 3-disubstituted oxindole group has been investigated. Perkin and Plant (J., 1923, 123, 676) that 9-acylhexahydro-10 : 11dihydroxycarbazoles (I; R = acyl), from the action of nitric acid on the corresponding acyltetrahydrocarbazoles (I1 ; R = acyl) in acetic acid, undergo a pinacolinic change on being heated alone or in acetic anhydride to give compounds which can readily be deacylated. Of the two alternative structures for the product, C,,H,,ON, the +doxy1 formulation (111) seemed the more probable at the time, and this was later supported by observations which are referred to below. It has more recently been shown by Plant and Robinson (Nature, 1950, 165, 36) that this view is untenable and that the substance must be cyclopentanespirooxindole (IV). Witkop ( J . Amer. Chem. SOC., 1950, 72, 614) independently reached the same conclusion, and Patrick and Witkop (ibid., p. 633) indirectly confirmed the oxindole formulation by showing that nitration of the material obtained by condensing 1-methyloxindole with tetramethylene dibromide gave a compound (V; R = Me) identical with the substance prepared by Perkin IT was observed by

The Kinetics of Oxidation of High Purity Nickel

“…A heat of activation of 41,200 cal/mole was ca[- culated from the slope for the temperature range of 500~176 This value is nearly in agreement with the work of Moore (10).…”

“…Using a volumetric method, Moore (10) studied oxidation of 99.9 % pure nickel over the temperature range of 400~-900~…”

New Spirocyclic Oxindole Synthesis Based on a Hetero Claisen Rearrangement

“…A one-proton doublet at δ 7.87 ( J = 8.0 Hz) is assigned to the proton at position 7 of the protected spirocycle. Confirmation of the structure was obtained by removing the carbamate protecting group to afford lactam 15 , whose analytical characteristics were identical to those previously reported for this material. , …”

“…Confirmation of the structure was obtained by removing the carbamate protecting group to afford lactam 15, whose analytical characteristics were identical to those previously reported for this material. 4,15 The [3,3] rearrangement takes place at low temperature. Thus, when the potassium enolate derived from 12 was allowed to stir at -78 °C for 1.5 h followed by quenching with cold methanol at that temperature, the only material observed in the 1 H NMR of the crude product mixture was rearranged 13.…”

The Thermochemistry And Reactivity Of Alkoxyl Radicals

“…These radicals are produced in the decomposition of cyclic compounds containing a bridged peroxide group. An example is provided by the thermal decomposition of dihydroascaridole (175). At 240°C.…”