I. Synthetic Studies on Tertiary Vinylogous Amides and Related Compounds. II. Cobalt(II) Chloride Complexes of Tertiary Vinylogous Amides and Related Ligands

Citation

Ellern, James Bernard (1974) I. Synthetic Studies on Tertiary Vinylogous Amides and Related Compounds. II. Cobalt(II) Chloride Complexes of Tertiary Vinylogous Amides and Related Ligands. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/0R6K-3R44. https://resolver.caltech.edu/CaltechETD:etd-10132005-080720

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. Tertiary vinylogous amides, both open-chain and cyclic, were prepared by several routes with a view toward their use as ligands for metal ions. It is shown that the thermodynamically preferred isomer (functionality trans) is the exclusive product in the open chain case. A new convenient synthesis of [beta]-aminobutenones is described. In contrast to previous studies, it was found that activated vinylidene chlorides (AVDC's) with [alpha]-hydrogen (Cl2C=CH-L, L = carbonyl function or cyano), react with certain secondary amines to give acetylenes, [...], either as intermediates or final products except with L = CHO. The mechanism of this reaction is discussed. A simple synthesis of 3,3-dichloropropenoic acid and its conversion to several functional derivatives are described. A case is presented for rotational isomerism in four [beta,beta]-dichlorovinyl carbonyl compounds. Nuclear magnetic resonance and infrared spectral correlations were made for the compounds prepared. In particular, it is shown that nmr spectroscopy allows ready distinction of piperidino vinylogous ureas from the isomeric acyl ketenaminals of this amine. Synthesis and partial characterization of complexes of some of the above polarized ethylenes and acetylenes with cobalt(II) chloride are reported. The polarized ethylenes behave somewhat like tertiary amides as ligands; in two cases, different forms of complex with same ligand were found. The "push-pull" acetylenes form 1:1 complexes in which the triple bond absorption(s) of the ligand is absent. The possible implications of this result are discussed.

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