Alkali metal fluorides alkyl halides

Because the [R2AI] cation can be stabilized by neutral Lewis bases, we assume that this is also true of ionogenic Lewis base alkali metal alkyls R-M. Thus, 1 2 complexes of alkali metal halides with aluminum trialkyls, especially fluorides, may dissociate (3a) into M and [R3AI-F-AIR3] , as shown by the moleeular structure in the crystalline state. Yet there is another possibility, shown in Scheme 3b, i. e., dissociation into aluminum-containing cations and anions. 

Studies on OCH(CF3)2, OCMe(CF3)2, OCMc2(CF3), and 0C(CF3)3 derivatives of the alkali metds, alkaline earth metals, transition metals, and the lanthanide elements are reviewed, with emphasis on work reported since 1988. Alkali and alkaline earth fluoroalkoxides are generally made from reaction between the alcohol and the metal, its hydride, or organometallics. Most syntheses of transition metal derivatives involve reaction between metal halides and alkali or alkaline earth salts, or the alcoholysis of metal alkyls, alkoxides and amides. Coordination between organic fluorine and electropositive metals (ie. Na, Ba, Tl, Pr) is often observed in the crystal structures of these fluoroalkoxides and may be related to their use as chemical vapor dqx)sition precursors for metal fluorides. 

In most processes recirculation of the stable feed hydrocarbon is maintained and the reactive olefin is fed into the recycling stream sometimes at several points. Thus, the concentration of olefin is always low and polymerization reactions are minimized. The alkylation reaction is favored by high pressures and low temperatures. However, in order to accomplish the reaction without catalysts, temperatures of 900 to 975 F are required.Polymerization also occurs rapidly at such temperatures, and hence the olefin concentration must be kept low. Thermal alkylation is conducted at 3,000 to 8,000 psig, whereas by means of catalysts such as sulfuric acid, boron fluoride, - aluminum chloride, double halides of alkali metals with aluminum, and hydrogen fluoride, pressures less than 500 psi and temperatures ranging from 450°F down to below zero may be employed. Sulfuric acid was widely used early in World War II as a catalyst in commercial installations, and a revival of interest has occurred since 1951. The process operates at 30 to 60 F for butenes and at substantially atmospheric pressure. The hydrofluoric acid process also proved during World War II to be a highly successful process, but only... 

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