Search results for "Hyponitrite"

Darstellung und Zerfall von tertiären Hyponitriten

1971

Dicumylhyponitrit (1a), substituierte Dicumylhyponitrite (1b1f) (p-Br, p-Cl, p-CH3, m-CH3, p-CH3O), Bis-[1.1-diphenyl-athyl]-hyponitrit (1h) und Bis-[1.1-dimethyl-pentyl]-hyponitrit (1g) wurden dargestellt. Die tertiaren Hyponitrite zerfallen bereits rasch bei-40 in Stickstoff und freie Alkoxyradikale, die dann zu den entsprechenden Alkoholen und Ketonen weiter reagieren. Die relativen Reaktivitaten von tert.-Butyloxy-und Cumyloxyradikalen hinsichtlich Wasserstoffabstraktion und β-Spaltung wurden fur verschiedene Losungsmittel bestimmt; Cumyloxyradikale neigen starker zur β-Spaltung als tert-Butyloxyradikale. Die freien Alkoxyradikale konnen Polymerisations- und Autoxydationsreaktionen init…

1976

tert-Butoxy radicals were generated by decomposing di-tert-butyl hyponitrite. The relative reactivities of substrates were measured from the ratio of tert-butanol and acetone formed. Polystyrene was found to be less reactive than model compounds. Activation parameters for the hydrogen abstraction reaction for cumene, 3-phenylpentane, and 2,4-diphenylpentane are reported and show small differences for the enthalpy of activation; large negative values for the entropy of activation demonstrate the importance of steric hindrance in the hydrogen abstracting step. 2,3-Diphenylbutane as model compound for head to head links in polystyrene exhibits low reactivity, whereas 2,5-diphenylhexane, a mode…

Trapping and Reactivity of a Molecular Aluminium Oxide Ion

2019

Aluminium oxides constitute an important class of inorganic compound that are widely exploited in the chemical industry as catalysts and catalyst supports. Due to the tendency for such systems to aggregate via Al‐O‐Al bridges, the synthesis of well‐defined, soluble, molecular models for these materials is challenging. Here we show that reactions of the potassium aluminyl complex K 2 [( NON )Al] 2 ( NON = 4,5‐bis(2,6‐diiso‐propylanilido)‐2,7‐di‐tert‐butyl‐9,9‐dimethylxanthene) with CO 2 , PhNCO and N 2 O all proceed via a common aluminium oxide intermediate. This highly reactive species can be trapped by coordination of a THF molecule as the anionic oxide complex [( NON )AlO(THF)] ‐ , which …