Halogens reactions with Alkali metals

VALUES OF RATE COEFFICIENTS FOR REACTIONS OF NON-HALOGENATED COMPOUNDS WITH ALKALI-METAL VAPOURS... 

Bromo-, 3-chloro-, 3-fluoro- and 3-iodo-oxetanes have all been prepared in good yield by the reaction of 3-oxetanyl tosylate with alkali metal halides in hot triethylene glycol (equation 70). Substitution reactions of the halogen atom have not been reported, except for the reaction of 3-iodooxetane with diethylamine. A low yield of 2-diethylaminooxetane was obtained from this reaction at 200 °C, but its chemical properties are not known (73JOC2061). 

Reactions at o -Position. Many studies have been concerned with the reactions of alkyl halides with cyanide in the presence of various metal ions, and with the direct alkylation of cyanide complexes. The classic synthesis of isonitriles was accomplished by the use of silver cyanide, whereas the corresponding reaction of organic halogen compounds with alkali cyanides yields nitriles (Equations 40 and 41) (34,36). 

The (3-diketonate chelate complexes are very stable and exhibit properties which are rather typical of aromatic systems. Many of their reactions such as halogenation, alkylation and acylation can be compared with those of the P-diketonate anions associated with alkali metal cations. However, complexes of transition and other metals add to the stability of the system, so that quite vigorous reaction conditions can be employed. In most of the work carried out on P-diketonate chelates, the modified ligand has not been removed from the metal ion, but this can usually be effected if desired. 

Reaction with Metals Halogens react with every metal in the periodic table to yield metal halides. With the alkali and alkaline earth metals, the formula of the halide product is easily predictable. With transition metals, though, more than one product can sometimes form depending on the reaction conditions and the amounts... 

The chemiluminescence, which is possibly best, understood is that emitted in the reaction of alkali metal vapours with halogens. When streams of alkali metal vapours and halogens at pressures of 10"2 to 10-3 nm Hg are mixed, alkali halides are formed with the emission of luminescence. The probable mechanism suggested is ... 

For the formation of cyclodisilazanes by salt elimination from silylamides =Si(X)-N(M)-(X = halogen, H M = alkali metal) two routes are discussed (i) intramolecular MX elimination and dimerization of the formed silanimine, (ii) intermolecular MX elimination to an intermediate =Si(X)-N(-)-Si(=)-N(M)- that immediately cyclizes with MX elimination [1-5]. The hydridosilylamides Me2(H)SiNLiR (R = Me2(H)Si, Me2CH, CMej) and RR (H)SiNLiSiMe3 (R, R = Me R = MesSiNH, Me3SiNLi, R = Me) react with MesSiCl in THF to give A -substitution products and in -hexane to form 1,3-cyclodisilazanes, formation of which has been explained via route (i) [6, 7], However, the silanimine has not been detected experimentally, Here we describe the synthesis of new hydridosilylamides and the reaction of these compounds and known hydridosilylamides with MesSiCl. 

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