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Competitive reactions of acetylketenes and N-propylacetimidoylketene with a variety of polar reagents were examined to provide reactivity information on these ketenes. Ab initio calculations on the addition of ammonia to formylketene are also reported. Reactivity trends show that acetylketene and acetimidoylketene are selective with alcohols in the presence of ketones. These observations support the planar, pseudopericyclic transition structures for these reactions which are predicted by ab initio calculations.