Advances in Catalysis, Vol. 2 by W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.)

By W.G. Frankenburg, V.I. Komarewsky, E.K. Rideal (Eds.)

With this moment quantity of Advances in Catalysis, the editors have endured their efforts to offer the various features of the catalytic approach. a couple of hugely certified males have contributed to this quantity. From the theoretical remedies of common approaches among molecules reacting at strong surfaces to the technically very important activities of fluoride catalysts, and to catalytic polymerizations of olefins, the reader becomes conversant in manifold rules and with a few commonplace experimental effects when it comes to catalytic phenomena. Our loss of an entire figuring out of catalytic motion, and our corresponding lack of ability to ''predict'' the way of attaining a wanted catalytic response, make it crucial for everybody operating during this course to familiarize himself with the event of others, whether such adventure was once collected in distant sectors of this tremendous box.

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5% 2-methyl-1-butene was copolymerized with propene in the presence of dihydroxyfluorboric acid a t 20” (Brooks, 43). The polymer was hydrogenated and distilled. 7 % unidentified. The formation of the octenes is indicated as follows C-C=C-C A C . C C - + H+ e C-&-C-C b++c=c-c*c-c- c: A K + A + H+ s C=C-C-C -C-C-C~C-C- L+ c: c-c-c (63) (84) 50 LOUIS SCHMERLING AND V. N. IPATIEFF At: Ll: C -H+ m. Conclusions. , 50). Its chief disadvantage is that it is not possible to predict which of several possible isomers will actually be obtained.

For reasons of convenience, the anions are not indicated but it must constantly be remembered that the negative portion of the ionic pair plays an essential, though lesser, role in the reaction. 30 LOUIS SCHMERLING AND V. N. CH3 I VI CH 3 VIII The two diisobutylenes, namely 2,4,4-trimethyl-l-pentene(VII) and 2,4,4-trimethyl-2-pentene(VIII), are produced in the ratio of about four to one in the presence of dilute sulfuric acid (McCubbin and Adkins, 22; Whitmore and Church, 23). The former is formed in larger amount because elimination of a proton from the methyl groups adjacent to the electron deficient carbon atom in VI takes place more readily than from the neopentyl group.

Ester Mechanisms a. Ester plus Olefin. A mechanism which is closely related to the carbonium ion mechanism assumes that the condensation takes place by way of addition of an alkyl ester to the olefin (Lwow, 52; cf. Kondakow, 53, and Katsuno, 54). The first step of the mechanism consists in ester formation by the reaction of the olefin with the acid, the addition occurring in accordance with Markowinkoff’s rule; the ester adds to another molecule of t,he olefin to form a higher molecular weight ester which then dissociates to form the polymer and regenerate the acid.

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