18218-27-4Relevant academic research and scientific papers
Stereochemistry of the Deamination of Spiropentylamine
Wiberg, Kenneth B.,Oesterle, Carmen
, p. 7763 - 7767 (2007/10/03)
The stereochemistry of the deamination of (-)-spiropentylamine in acetic acid has been studied, and it was found that one of the major products, (-)-spiropentyl acetate, was formed with essentially complete inversion of configuration. This suggests that it is formed via an SN2 displacement on the spiropentyldiazonium ion. The stereochemistry was established by the conversion of (-)-spiropentanecarboxylic acid to (-)-spiropentylamine via a Curtius rearrangement that proceeds with retention of configuration. The (-) acid also was converted to spiropentyl methyl ketone with methyllithium and then to (+)-spiropentyl acetate via the Baeyer-Villiger reaction that also results in retention of configuration. The deamination of N-nitroso-N-spiropentyl urea was studied in methanol, and spiropentyl methyl ether was a major product. Similarly, the reaction in water led to spiropentanol. The latter reactions also lead to 2-methoxymethyl- or 2-hydroxymethyl-1,3-butadiene, respectively, corresponding to the alternative mode of reaction via a cyclopropyl cation-allyl cation rearrangement.
REACTIONS 0F PROPELLANE
Zefirov, N. S.,Surmina, L. S.,Sadovaya, N. K.,Blokhin, A. V.,Tyurekhodzhayeva, M. A.,et al.
, p. 2002 - 2014 (2007/10/02)
The photochemical reactions of propellane with bromine, dioxane dibromide, iodine, (dichloroiodo)benzene, methyl iodide, carbon tetrabromide, bromoform, and tributyltin hydride take place by a radical mechanism and lead to the formation of the products from addition at the central bond, i.e., 1,3-substituted bicyclopentanes.In the photochemically initiated reactions of chloroform, carbon tetrachloride, and bromomalonic ester with propellane compounds with the structure of 1,1'-bis(bicyclopentane) are formed in significant amounts in addition to the above-mentioned compounds.The addition of hydrogen bromide with irradiation leads to the brominated derivatives of cyclopropane and cyclobutane.The formation of cyclobutane derivatives is also observed in the reactions with such reagents as bromine or dioxane bromide (with irradiation) and 2-nitrobenzenesulfenyl chloride (in the presence of atmospheric oxygen).In the course of the reaction of propellane with electrophilic reagents (mercuric acetate, tripropyl- and triallylboranes) ring cleavage occurs, and derivatives of methylenecyclobutane are formed.
Vibrational Spectrum, Structure, and Energy of Propellane
Wiberg, Kenneth B.,Dailey, William P.,Walker, Frederick H.,Waddell, Sherman T.,Crocker, Louis S.,Newton, Marshall
, p. 7247 - 7257 (2007/10/02)
The structure of propellane (bond lenghts and angles) was determined from an analysis of the rotational components of the infrared bands of the parent compound and of its d6 derivative, and it was found to be in good agreement with the structure ca
