As part of a comprehensive investigation on the stereochemical aspects of base-catalyzed 1,2-elimination reactions, we have studied a set of acyclic carbonyl substrates that react by an irreversible E1cB mechanism with largely anti stereospecificity. (2)H NMR data show that these reactions using KOH in EtOH/H(2)O under non-ion-pairing conditions produce a minimum of 85-89% anti elimination on stereospecifically labeled tert-butyl (2R*,3R*)- and (2R*,3S*)-3-(3-trifluoromethylphenoxy)-2,3-(2)H(2)-butanoate, S-tert-butyl (2R*,3R*)- and (2R*,3S*)-3-(3-trifluoromethylphenoxy)-2,3-(2)H(2)-butanethioate, and the related ketones, (4R*,5R*)- and (4R*,5S*)-5-(3-trifluoromethylphenoxy)-4,5-(2)H(2)-3-hexanone. With both diastereomers of each substrate available, the KIEs can be calculated and the innate stereoselectivities determined. The elimination reactions of the β-3-trifluoromethylphenoxy substrates occur by E1cB mechanisms with diffusionally equilibrated enolate-anion intermediates. Thus, it is clear that anti elimination does not depend solely upon concerted E2 mechanisms. Negative hyperconjugation provides a satisfactory explanation for the anti stereospecificity exhibited by our carbonyl substrates, where the leaving group activates the anti proton, leading to the enolate intermediate. The activation of the anti proton by negative hyperconjugation may also play a role in the concerted pathways of E2 mechanisms. We have also measured the rates of the hydroxide-catalyzed elimination reactions of butanoate, thiobutanoate, and ketone substrates in EtOH/H(2)O, with β-tosyloxy, acetoxy, and 3-trifluoromethylphenoxy nucleofuges.
Eager to move on after the divisiveSonderwegdebates of the 1980s, historians of modern Germany have been busily elaborating a new central narrative around the notion of biopolitics. Aimed at producing a more powerful and productive society by regulating, optimizing, and even exterminating specific human populations, biopolitics has encompassed everything from housing reform, anti-smoking campaigns, and child vaccination programs to pro- and anti-natalist tax policies, national census taking, and the science of industrial hygiene. Identified by Michel Foucault and others as a general feature of all Western modernities, biopolitics has been a particularly fruitful concept for German historians, who have used it to trace the evolution of racial hygiene—the Nazi variant of eugenics and Germany's most infamous application of biopolitical principles—from a politically diverse group of Wilhelmine and Weimar social reformers. The very normality of these reformers, given the international context, has in turn allowed scholars to avoid labeling German modernity as deviant while at the same time framing the murderous dynamic of the Nazi years as a potential latent in modernity more generally. As Edward Ross Dickinson put it in an excellent review article recently, Germany has emerged from this reevaluation “not as a nation having trouble modernizing, but as a nation of troubling modernity.”
This article traces the emergence of the health narrative as a new genre of bodily knowledge in late nineteenth- and early twentieth-century Germany. Health narratives were life stories told by or about an individual, either real or fictional, who made conscious choices about how to conduct their bodily existence. Pioneered by lay health seekers known as life reformers, health narratives were co-opted by physicians hoping to reinvent medical enlightenment for the twentieth century. In addition to surveying the variety of forms that health narratives took in adult and children’s literature, the article explores the paradoxes and contradictions that ensued around voice, agency, embodiment, and selfhood as these narratives spread from life reform to medical contexts.
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