Tools
Tools
Gates, Peter Norman (1964) Study of the interaction of the boron trihalides with ketones. Doctoral thesis, Northern Polytechnic.
Reactions of acetone with boron trichloride in varying proportions were investigated. Decomposition of the 1:1 complex afforded hydrogen chloride and a red resinous solid containing chlorine and boron. Highly unstable addition products containing more acetone than required for the 1:1 complex were obtained and these all decomposed to give 2-chloro-2-methylpentan-4-one, mesityl oxide, hydrogen chloride and a boron-containing residue. Similar compounds were obtained from the decomposition of 3:1 ketone: boron trichloride addition products from ethyl methyl and diethyl ketones. Analogous products were obtained from aryl ketones. The products are apparently formed by the reaction of free ketone with a boron-containing compound, the nature of which is not certain. No organoboron compounds of a type previously prepared from aldehyde-boron trichloride reactions were obtained.
Several new 1:1 complexes of ketones with boron trihalides were prepared and the donor-acceptor properties correlated with infrared (boron-oxygen and carbonyl stretching frequencies) and nuclear magnetic resonance (1H and 11B resonance) spectra. The spectroscopic properties were all consistent with the known order of acceptor power of the boron trihalides towards other donors.
Thirty ketone-boron trifluoride complexes (seventeen of which are new) and four ether-boron trifluoride complexes were prepared. Where possible, correlations were made between spectroscopic data (1H, 19F and 11B resonances and carbonyl, boron-oxygen and boron-fluorine stretching frequencies) and known donor-acceptor properties of the complexes. Independent data on these systems is rare but it appears that the 19F and 11B resonances and the boron-oxygen stretching frequency especially may give a useful measure of the strength of the donor-acceptor interaction. The spectroscopic results are discussed in terms of the various electronic and steric factors which affect the donor-acceptor interaction.
A gas-liquid chromatographic method was developed for the analysis of straight-chain halooctanes and halopentanes which are produced in reactions of some octyl and pentyl derivatives with Lewis-acids (Appendix).
 |
View Item |