The ready change of isobutyl compounds to tertiary butyl compounds has long been known. The interconversion of the bromides has been thoroughly studied.2 The results of these studies indicate that (1) rearrangement of isobutyl bromide to tertiary butyl bromide at high temperatures in the vapor phase may occur by way of dissociation and addition of hydrogen bromide (Brunei) but (2) this rearrangement takes place more readily in the liquid phase and at temperatures at which there is no dissociation into hydrogen bromide and olefin. Heating the vapor of isobutyl bromide at 140°for fourteen hours produces no rearrangement while heating the liquid at the same temperature for one hour gives a 55% conversion to the tertiary bromide (Michael). The isobutyl "ions" readily rearrange by the transfer of an electron pair and its proton.3Other isobutyl compounds undergo similar rearrangements. Isobutyl iodide reacts with silver acetate in the absence of a solvent to give isobutyl acetate while the presence of acetic acid as a solvent makes tertiary butyl acetate the chief product.4 Similar results are obtained with silver cyanate.6 With silver oxide in the presence of acetic acid, isobutyl bromide yields tertiary butyl alcohol and tertiary butyl acetate (Linnemann). An even more interesting example of this transformation is the conversion of isobutyl iodide to tertiary butyl chloride by the action of iodine monochloride (Linnemann). This reaction apparently occurs as follows (CH3)2CHCH2 Í:The two ions left are peculiar in that each is the result of a "chemical reaction" rather than of an ordinary "ionization."Each is present only in 1 Presented by Albert R. Lux in partial fulfilment of the requirements for the Ph.D.
The dielectric relaxation of water rich aqueous solutions of ethanol, ehtylene glycol, glycerol, diethylene glycol, 1,2-butanediol, 1,3-butanediol and 1,4-butanediol has been measured at 20 °C. In all cases the fitting of the data by a sum of Debye type spectral components allows for two description modes which can be interpreted as a collective alteration of the water relaxation or, on the other hand, as formation of a microheterogenous solution where "affected" and "unaffected" water becomes discernible.
2994lbb mviN smith and album r. lux Vol. 51 dye) and the extremely soluble l-amino-4-phenol-sulfonic ester (0.46 mole per mole of dye). The yield ratio of the latter two products was identically the same as obtained in the cleavage of the unsulfonated dye.Cleavage of 4-Hydroxyazobenzene-4-sulfonic Acid at 140 to 145°.-The sodium salt of the dye and sodium sulfite solution of approximately 0.75 M concentration were heated in a steel autoclave at 140 to 145°. At the end of twenty hours cleavage was found complete. Analytical determinations yielded very nearly the same results: 3.6% of the consumed sulfite was changed to sulfate, a little more than was formed at the lower temperature. Summary 1. A new type reaction of monoazo dyes has been observed. They combine with two moles of a neutral sulfite, in solution, suffering cleavage into a primary amine and the salts of N-sulfonic and N-disulfonic acids.2. 4-Hydroxyazobenzene yielded approximately 0.78 mole of aniline, 0.22 mole of an N-sulfonic acid of aniline, 0.78 mole of an N-disulfonic and 0.22 mole of an N-monosulfonic acid of l-amino-4-phenol and no trace of unsulfonated aminophenol.3. 4'-Hydroxyazobenzene-4-sulfonic acid reacted similarly, sulfanilate being formed as a result of cleavage.4. Hydrolysis and rearrangement of free N-sulfonic acids resulted in complete recovery of the primary dye component in its original form; the secondary component yielded l-amino-4-phenol-5-sulfonic acid and an extremely soluble, stable l-amino-4-phenol-sulfonic ester, a compound not previously reported.5. An explanation of the cleavage reaction has been suggested, founded on an assumption of functional differences between the two nitrogen atoms of the azo group.
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