Zur Kenntnis der Sexualhormone I. Über die Gewinnung von 3‐Chlor‐ und 3‐Oxy‐ätio‐allocholanon‐(17). Synthese einer Verbindung von den Eigenschaften des Testikelhormons

Růžička, L.; Goldberg, M. W.; Brüngger, H.

doi:10.1002/hlca.193401701169

Cited by 57 publications

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“…These procedures are all hydrolytic and several involve equilibrium reaction of hydroxylamine with a more reactive carbonyl compound, They may take a number of hours to go to equilibrium or completion. Common hydrolytic procedures especially applicable to semicarbazoiles include sulfuric acid in ethanol (2), sulfuric acid in dloxane (3,4) hydrochloric and acetic acids (5), and sodium nitrite and acetic acid (8). Some of the procedures are drastic and can lead to condensation products or hydrolysis of sensitive protecting groups such as acetoxy groups.…”

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confidence: 99%

Preparative conversion of oximes to parent carbonyl compounds by cerium(IV) oxidation

Bird¹,

Diaper²

1969

Can. J. Chem.

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Oximes and semicarbarones are oxidized by ceric ammonium nitrate to the parent carbonyl cornpound in good yield. Suitable solvent systcms includc aqucous alcohols, acetonitrile, and acetic acid. The reaction is rapid at 0" or below. This procedure for regeneration of aldehydes and ketones from these derivatives may be preferable to the well-known hydrolytic procedures in some cases. The stoichiometry of the reaction was studied by isothermal calorimetry; two equivalents of oxidant are consumed by one mole of oxime evolving approximately 40 kcal/mole. A smaller consunlption of oxidant by hexane-2,s-dione dioxinie was attributed to stabilization of the monoxime as a nitroso chelate. Gaseous products were studied by infrared spectroscopy and nitrous oxide was identified as the sole product absorbing between 3 and 15 p. A reaction mechanism is proposed involving one-electron oxidation to the iminoxy radical, oxidized by a second one-electron step to the cc-hydroxy nitroso compound. Dimerization and elimination of hyponitrous acid gives the carbonyl compound. Nitrocyclohexane was absent from the oxidation product from cycIohexanone oxime. Carvone oxime was oxidized to carvone without racemiration or significant attack of the olefin groups.

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confidence: 99%