Directive effects in the sulfonation of iodobenzene :|banionic hyperconjugation and lithium amides ; high pressure studies on organic compounds


The isomer distribution in the sulfonation of iodobenzene at -12.5°C. with sulfur tr~oxide (S-35) in liquid sulfur dioxide was found to be 1.40 ± 0.11% ortho, 0.34 ± 0.11% meta, and 98.26 ± 0.11% para. Pure sodium salts of each of the isomers were made from the corresponding aminobenzenesulfonic acids. After dilution with an aliquot of the sulfonation mixture, the salts were purified by recrystallization and were counted by liquid scintillation counting. Attempts to determine the relative rate of sulfonation between toluene and iodobenzene failed. The radioactive sodium p-iodobenzene sulfonate could not be separated from sodium p-toluenesulfonate by recrystallization. The lithium amides of methylamine, ethylamine, isopropylamine, tert-butylamine and 2-aminopropane-2-d were prepared from phenyl lithium and the amines. Infrared spectra of the amides were scanned in the C-H region. Comparison of the spectra of the amides and the amines showed no shifts like those found for the corresponding alcohol-alkoxide spectra. It was therefore concluded that anionic hyperconjugation could not account for the shift in the spectra of the alcohol-alkoxide system. The behavior of cyclooctatetraene, the silver adduct of cyclooctatetraene, norbornadiene, diphenylacetylene, tetraphenylcyclobutadiene-palladium chloride and ferrocene was studied under high pressures ranging from 15 to 55 kats. and with temperatures from 25 to 850°C. This work was carried out with Hall's tetrahedral anvil apparatus. If the temperature was high enough each of these compounds was found to decompose. When the temperature was below the decomposition temperature, cyclooctatetraene, diphenylacetylene and norbornadiene polymerized. No evidence of a valence tautomerization was found. The silver adduct of cyclooctatetraene and tetraphenylcyclobutadiene-palladium chloride decomposed at high temperatures. No other results were noted with these two compounds. Ferrocene underwent decomposition by iron catalysis to a mixture of iron carbides at pressures from ambient to 55 kats. and temperatures above 500°C. The same products were observed if no iron was added and the temperature and pressure were 55 kats. and 800°C., respectively. A preliminary spectrophotometric study of benzonitrile in 25%-ethyl alcohol-75% water was carried out. Cupric bromide and hydrobromic acid or cupric chloride and hydrochloric acid were added to constant ionic-strength solutions of benzonitrile. No evidence was found in the ultraviolet region for any complex ion formation. The same results were found for p-fluorobenzonitrile.



College and Department

Chemistry and Biochemistry



Date Submitted


Document Type





Sulfonation, Benzene, Molecules, Lithium, High pressure (Science), Research



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