Reactions of 5-alpha-hydroxy steroids. VII. The westphalen rearrangement of some 3-beta-substituted-6-beta-acetoxy-5-alpha-hydroxy cholestanes.
Abstract Product analyses and kinetic studies of the reactions of 3β-substituted-6β-acetoxy-5α-hydroxy cholestanes with H 2 SO 4 -Ac 2 O-AcOH reveal a marked dependence of the reactions upon the nature of the 3β-substituent.
Chapter 29. Steroids
Publisher Summary This chapter elaborates the development and preparation of steroids. Preliminary reports on a new fragmentation of α,β-epoxy ketones to acetylenes and carbonyl-containing products showed that the reaction can be of general application. Tosylhydrazones on reaction with alkylithium reagents give olefins in high yield. This new synthesis allowed for example the preparation of 16-androstene from androstan-17-one in quantitative yield. Reduction of carbonyl functions to methylene can be effected electrochemically or by treatment of the steroid ketones with powdered zinc in acetic anhydride saturated with hydrogen chloride at room temperature. A convenient method for transposing the oxygen of a carbonyl to an adjacent methylene involved condensing the ketone with an aromatic aldehyde, reduction of the resulting arylidene ketone with lithium aluminum hydride-aluminum chloride reagent to the corresponding desoxy compound, followed by ozonolysis to the new ketone. The Westphalen rearrangement of some 3β-substituted-6β-acetoxy-5α-hydroxycholestanes has also been studied and the products and kinetics are shown to be dependent on the nature of the 3-substitutents.
Nietzsche: Philosopher, Psychologist, Antichrist
This classic is the benchmark against which all modern books about Nietzsche are measured. When Walter Kaufmann wrote it in the immediate aftermath of World War II, most scholars outside Germany viewed Nietzsche as part madman, part proto-Nazi, and almost wholly unphilosophical. Kaufmann rehabilitated Nietzsche nearly single-handedly, presenting his works as one of the great achievements of Western philosophy. Responding to the powerful myths and countermyths that had sprung up around Nietzsche, Kaufmann offered a patient, evenhanded account of his life and works, and of the uses and abuses to which subsequent generations had put his ideas.Without ignoring or downplaying the ugliness of many of Nietzsche's proclamations, he set them in the context of his work as a whole and of the counterexamples yielded by a responsible reading of his books. More positively, he presented Nietzsche's ideas about power as one of the great accomplishments of modern philosophy, arguing that his conception of the "will to power" was not a crude apology for ruthless self-assertion but must be linked to Nietzsche's equally profound ideas about sublimation.He also presented Nietzsche as a pioneer of modern psychology and argued that a key to understanding his overall philosophy is to see it as a reaction against Christianity. Many scholars in the past half century have taken issue with some of Kaufmann's interpretations, but the book ranks as one of the most influential accounts ever written of any major Western thinker.