Chloroform reaction + alkali atoms

The effect of the benzene ring on the combining power of the adjacent carbon atom here shows itself with special clarity. Whereas chloroform is rather resistant towards alkalis, benzotrichloride is hydrolysed by them with extraordinary ease all three chlorine atoms are removed and benzoic acid is produced. It would be wrong to think, however, that in this reaction all the chlorine is removed at the same time in accordance with the equation ... 

Halocarbons have been used successfully as a source of carbide atoms in the synthesis of carbido clusters of rhodium and nickel. For example, [RhgCCCO) ] may be synthesized by the reduction of Rh4(CO)i2 with alkali hydroxide in methanol followed by reaction with chloroform 184), or by the reaction of [Rh(CO)4] with CCI4 according to Eq. (1). 

The alkali metals are easily vaporized at temperatures of 300—500"C, and most studies of this group have been reviewed in Sections 2 and 3. The reactivity of alkali metals in co-condensation reactions is high, but little different from that in diffusion flame studies. However, the alkali metals have been used in a number of low-temperature reactions, largely to produce radicals or intermediates of spectroscopic interest. For example, the trichloromethyl radical has been produced in a solid argon matrix by reaction of lithium atoms with carbon tetrachloride [294]. A similar technique has been used to produce the CBr2H radical from bromoform [295], the CCljH radical from chloroform [296], and the methyl radical from methyl iodide and methyl bromide [297]. In all these cases the corresponding lithium halide is produced. 

Certain compounds which contain halogen, other than acyl chlorides, react with amines and form condensation-products as the result of the elimination of a hydrogen halide. The reaction of methylamine with chloroform, CHCI3, in the presence of an alkali is an example of a reaction of this type. In this case, both hydrogen atoms joined to nitrogen unite with chlorine to form hydrochloric acid, and an intermediate compound is probably formed, which is unstable and loses another molecule of the acid. The steps in the reactions may be represented by the following equations —... 

With benzoyl chloride in alkali, 4-pyridthione gives 4-benzoylthiopyri-dine, whilst acetic anhydride causes N-acetylation i, Some interesting reactions occur in the ethoxycarbonylation of 4-pyridthione. With ethyl chloroformate in ethanol, reaction occurs at the sulphur atom, whilst in sodium bicarbonate solution the nitrogen atom is attacked i ... 

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