Polymerization. XII. The Metalation of Olefins and Dienes and their Use in Alfin Polymerization of Butadiene¹

Abstract

METALATION OF OLEFINS AND DiENES IN ALFIN POLYMERIZATION 3786potassium dodecanoate indicate that the transition occurs with the CS alcohol, but additional evidence, now being obtained, will be necessary before more definite ideas as to the extent of penetration of these long chain alcohols into the soap micelle can be advanced. SummaryAdditional evidence as to the presence of two loci of solubilization in soap micelles is obtained from solubilization data of hydrocarbon and polar compounds in soap solutions containing added electrolyte. The addition of potassium chloride to a 0.32 N potassium tetradecanoate (KCLO solution results in an enhancement of solubility of n-heptane and a decrease of n-octanol. With 0.05 N KC14-KC1 solutions, the solubilities of both polar and non-polar compounds increase. However, after the initial increase up to about 0.50 N potassium chloride, the solubility of the alcohol again decreases. Even though the critical micelle concentration of a soap depends only on the equivalent concentration of the ion opposite in charge to that of the colloidal electrolyte, the nature of both anion and cation affect solubilization. Thus in the solubilization of n-heptane for equivalent concentrations of additive, KC1 > K&OI > K4Fe(CN)6.3HpO whereas the reverse order holds when n-octanol is solubilized. However, these latter data present additional proof as to the two loci of solubilization, one in the bydrocarbon center of the micelle, the other in tbe palisade layer in the region occupied by the soap molecules. As the chain length of the solubilized alcohol is increased, there is a gradual transition from polar type to non-polar type solubilization most strikingly indicated when comparing Ca and CIO alcohols. Qualitative measurements of viscosity indicate that the addition of very small amounts of long chain alcohols to soap-salt systems result in the formation of very viscous, almost gel-like, systems. The maximum viscosities always QCCW a t concentrations of alcohol below the limit of solubilization (as indicated by turbidity).ST. PAUL, MINK.

CONDENSATIONS BY SODIUM. XXXVIII. THE METALATION OF tert-BUTYLBENZENE BY AMYLSODIUM AND THE EFFECTS OF ASSOCIATED SALTS1, 2

“…The apparatus and general technique used in this study are the same as are regularly employed (1,2,3,11) in this program of work. The apparatus and general technique used in this study are the same as are regularly employed (1,2,3,11) in this program of work.…”

200 Years of Lithium and 100 Years of Organolithium Chemistry

“…The first reason lies in the tendency to undergo Wurtz‐Fittig C–C coupling reactions when organic halides are treated with elemental sodium or potassium. Although a few examples are reported for the successful direct synthesis of alkylsodium the broad application was limited by demanding synthetic requirements. Secondly, the solubility of alkyllithium is in almost every case better in comparison to its corresponding sodium or potassium counterpart.…”

Organosodium and Organopotassium Compounds Part I: Properties and Reactions

“…On the other hand, its structure is quite different from that of the polymer obtained by the free-radical process using azobisbutyronitrile [203]. Polymerizations promoted by alfin catalysts [59,207] or Zieglei-catalysts [ZOS] cannot be discussed here.…”

“…Accordingly, alkali alkyls replace an olefinic hydrogen by a metal atom, provided that, as in ethylene [59] or 3,3-dimethyl-l-butene [59], more readily metalated allylic hydrogens are absent.…”