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Conductivities of Dodecyland Octadecylamines 97 sample crystallized from the same solvents in broad colorless needles, m. p. 39-40.5°.

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of magnesium is very marked. The simplest explanation is that, in the case of the aromatics, the anion is sometimes discharged to give an aryl halide instead of the free radicals (R2MgX2)-+ R X + RMgX + 2eThe RX would then M u s e over to the cathode and react with the magnesium deposited there to produce more Grignard reagent, so that the net result of the electrolysis would be zero. The eating away of the magnesium by aryl halide would account for its appearance.In order to test the above mechanism, phenylmagnesium bromide was electrolyzed in a transference cell where diffusion was avoided. As would be predicted, the magnesium in the cathode portion was gray and unreactive. The anode portion was drained off and found to contain appreciable amounts of bromobenzene. A portion of the Grignard before electrolysis contained no unreacted bromobenzene.The increased tendency of aryl Grignards to give this secondary reaction, where a halide is formed, may be due to the greater strength of the carbon to halogen bond. It is significant that this reaction is not found in the cases where the Wurtz-Fittig type of reaction occursThe observed vigorous attack on hydrogen bearing substances by the aryl radicals is probably related to the fact that the concentration of free radicals a t any instant is very low due to the secondary anode reaction outlined above. Both the coupling and disproportionation of phenyl free radicals in the absence of a solvent have been r e p~r t e d .~ In general, the evidence indicates that the aryl radicals axe more diffcult to form and once formed, are more reactive than the aliphatic free radicals of simple nature. Summary1. The products of electrolysis of phenyl-, p-tolyl-, p-chlorophenyl-and benzylmagnesium bromides are reported.The alternative discharge of aryl halides as an anode reaction is shown to occur with aromatic Grignard reagents.3. The behavior of short-lived aryl free radicals in ether solution is discussed and mechanisms advanced for their reactions.The marked difference between aliphatic and aromatic Grignards upon electrolysis is brought out. EVANSTON, ILLINOIS 2. 4.The behavior of the acetates of dodecylamine and octadecylamine in water is qualitatively similar to the behavior of the corresponding hydrochlorides in water.l A study of the cooling curves coupled with visual observations of both the dodecylamine acetate-water system and octadecylamine acetate-water system show that they both exhibit colloidal properties over a wide range of temperature and concentration. Determination of the osmotic coefficient g and dew-point data further substantiate the colloidal behavior of these systems. Dodecylamine acetate is more soluble in water than octadecylamine acetate. A metastable region was observed in the case of octa-(1) Ralston, Hoffman, &err and Selby, THIS JOURNAL, 63, 1598 (1941).HOERR AND EVERETT J. HOFFMAN decylamine acetate and water but not in the dodecylamine ace tate-water system. This differs from the corresponding hydrochlorides where the metastable region was observed on...

solved in 95% alcohol and to this mixture was added '/IO of its volume of conc. hydrochloric acid. On standing the diurethane separated in 90% yield. It forms h e , white crystals from alcohol, is nearly insoluble in hot water and melts a t 1 9 0 ' .