Halogen compounds, reaction with alkali metals

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

The diffusion cloud (flame) technique developed by Hartel and Polanyi in the 1930s is one of the early methods of studying rapid bimolecular chemical reactions imder pseudo-first-order, steady-state conditions. This method is the source of most measured rates for reactions of alkali metals with halogenated compounds and still serves as a basis for experimental and theoretical studies. In most applications of the technique, sodium metal is heated in an oven, mixed with an inert carrier gas, and allowed to diffuse into a backgroimd of a reactant gas. In very exothermic reactions the sodium flame is chemiluminescent otherwise the cloud is illuminated with a sodium resonance lamp. The reaction rate can be measured either by determining the distance the sodium diffuses until it all reacts or by spectroscopically measuring the total amount of sodium in the cloud. ... 

Halogenated hydrocarbons are stable compounds with low reactivity. The explosion hazard is low and reported cases are rare. These compounds, however, may react violently with alkali metals such as sodium or potassium and their alloys, or with finely divided magnesium, calcium, aluminum, or zinc. Explosions may occur when mixtures are either heated or subjected to impact. Violent reactions may occur with powerful oxidizers. 

Carbon tetrachloride is a noncombustible liquid. Explosion may occur when this compound is mixed with alkali metals such as sodium, potassium, lithium, or their alloys or finely divided aluminum, magnesium, calcium, barium, beryllium, and other metals on heating or impact. Reactions with hydrides of boron or silicon, such as diborane, disilane, trisilane, or tetrasilane, can be explosively violent. When mixed with dimethyl formamide and heated, carbon tetrachloride may explode (Kittila 1967). Its mixture with potassium terf-butoxide may ignite. Its reaction with fluorine or a halogen fluoride is generally vigorous and may become violent on heating. A violent reaction occurs with hypochlorites. 

The fundamental theory of phase transfer catalysis (PTC) has been reviewed extensively. Rather than attempt to find a mutual solvent for all of the reactive species, an appropriate catalyst is identified which modifies the solubility characteristics of one of the reactive species relative to the phase in which it is poorly solubilized. The literature on the use of PTC in the preparation of nitriles, halides, ether, and dihalocarbenes is extensive. Although PTC in the synthesis of C- and 0-alkylated organic compounds has been studied, the use of PTC in polymer synthesis or polymer modification is not as well studied. A general review of PTC in polymer synthesis was published by Mathias. FrecheE described the use of PTC in the modification of halogenated polymers such as poly(vinyl bromide), and Nishikubo and co-workers disclosed the reaction of poly(chloromethylstyrene) with nucleophiles under PTC conditions. Liotta and co-workers reported the 0-alkylation of bituminous coal with either 1-bromoheptane or 1-bromooctadecane. Poor 0-alkylation efficiencies were reported with alkali metal hydroxides but excellent reactivity and efficiencies were found with the use of quaternary ammonium hydroxides, especially tetrabutyl- and tetrahexylammonium hydroxides. These results are indeed noteworthy because coal is a mineral and is not thought of as a reactive and swellable polymer. Clearly if coal can be efficiently 0-alkylated under PTC conditions, then efficient 0-alkylation of cellulose ethers should also be possible. 

A number of compounds of the types RBiY2 or R2BiY, where Y is an anionic group other than halogen, have been prepared by the reaction of a dihalo- or halobismuthine with a lithium, sodium, potassium, ammonium, silver, or lead alkoxide (120,121), amide (122,123), a2ide (124,125), carboxylate (121,126), cyanide (125,127), dithiocarbamate (128,129), mercaptide (130,131), nitrate (108), phenoxide (120), selenocyanate (125), silanolate (132), thiocyanate (125,127), or xanthate (133). Dialkyl- and diaryUialobismuthines can also be readily converted to secondary bismuthides by treatment with an alkali metal (50,105,134) ... 

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). 

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