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The structure of the acenaphthene-1,2-diol dinitrates and their reaction with pyridine Csizmadia, Imre

Abstract

Calculation of bond angles from the available X-ray diffraction data for acenaphthene, indicated that the five-membered ring is planar and that cis-1,2-substituents are fully eclipsed and transsi.2-rsubstituents fully staggered in this ring system. These conclusions were confirmed by the ease of formation of cyclic carbonate and isopropylidene derivatives of the cis-acenaphthene-1,2-diol and the failure of the trans-isomer to form these new derivatives. The presence of intramolecular hydrogen bonds in the crystalline cis-diol and the absence of such bonds in the trans-diol also supported this structure. A single carbonyl stretching frequency of 1718 cm⁻¹ was found in the spectrum of pure acenaphthenequinone and the reported second band around 1770 cm⁻¹ was shown to be due to an impurity. A linear relation of the C=O and C-O-C stretching frequencies of the cis- and trans- diacetate and dibenzoate esters of the acenaphthene-1,2-diols was determined and compared with a similar relationship found for steroid esters. The dinitrate esters of the cis- and trans-acenaphthene-1,2-diols were prepared and characterized and the rates of their reactions with anhydrous pyridine were compared with!:those of other cyclic diol dinitrates. The dinitrates decomposed in a first order reaction with half lives of 90 and 610 minutes for the trans- and cis- isomers respectively at 25°C. A combination of chromatographic and spectrophotometry techniques was developed for rapid and accurate analyses of mixtures containing nitrate esters. An ultramicro-Kjeldahl procedure was developed for the determination of covalent nitrate nitrogen on a microgram scale.

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