Dissertation in organic chemistry.|nPart I.|pThe fate of the anilino moiety in the rearrangement of α-anilonoketones.|nPart II.|pPartial rate factors for sulfonation of bromebenzene with sulfur trioxide.|nPart III.|pPreliminary survey on the effect of high pressure on ferrocene and cycloöctatetraene


Part I. The rearrangement of α-anilinoketones was studied in an effort to determine the mode of movement of the nitrogen moiety. A crossover experiment was carried out with an equimolar mixture of 2-(4- bromoanilino)-1-(4-bromophenyl)-2-(4-methoxyphenyl) ethanone and 2-(4-chloroanilino)-1-(4-chlorophenyl) -2-(4-methoxyphenyl)ethanone with γ- picoline hydrobromide as the catalyst. The reaction product was analysed by means of a mass spectrograph. The results of the analysis indicate a crossover of the nitrogen moiety during rearrangement. This indicates that the nitrogen moiety moves in an intermolecular manner during the rearrangement. Part II. The isomer distribution from the sulfonation of bromobenzene with sulfur trioxide was determined by the isotope dilution technique. Bromobenzene was sulfonated with labeled sulfur trioxide (S-35) in refluxing sulfur dioxide and aliquots of the reaction mixture were added to equimolar quantities of the pure isomeric bromobenzenesulfonic acids. Each isomer was then recrystallized until a constant count rate was obtained. The isomer distribution was then obtained by comparing the activity of the individual isomers to the sum of the activities of all three isomers. This gave the following results: Ortho, 0.6 ± 0.2; Meta, 3.6 ± 0.8; Para, 95.9 ± 0.6. A competitive sulfonation between bromobenzene and toluene was run using sulfur trioxide (S-35) in liquid sulfur dioxide as the sulfonation agent. An isotope dilution technique was used to obtain the relative amounts of sulfonated bromobenzene and toluene in the reaction mixture. The relative rate of sulfonation of toluene to bromobenzene is 9.4. Comparing this with the toluene-benzene rate ratio of 29.5 gives a bromobenzene-benzene rate ratio of 3.1. Part III. Cycloöctatetraene and ferrocene have been submitted to very high pressure (up to 92 kiloatmospheres) and in the case of ferrocene moderate temperatures have been simultaneously applied (up to 900° C.). Cycloöctatetraene when held at pressures in excess of 54 kiloatmospheres for longer than one hour breaks down into a transparent solid and low boiling liquid. The identities of the solid and liquid have not been determined. Ferrocene breaks down into a mixture of iron carbides as shown by the x-ray powder pattern. This breakdown occurs at 605°C. at a pressure of 24.3 kiloatmospheres and the temperature of decomposition is proportional to the pressure with a proportionality constant of 0.74 kiloatmosphere/°C.



College and Department

Chemistry and Biochemistry



Date Submitted


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Chemistry, Organic, Sulfonation, High pressure (Science), Research



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