Lists
Lists
Tolcher, P. H. (1954) Interaction of branched alcohols with inorganic non-metallic halides. Doctoral thesis, Northern Polytechnic.
An attempt has been made to correlate the existing data on the conductivity of, and solubility of hydrogen halides in alcohols. The information gained is used, in conjunction with previous kinetic investigations into the reaction between alcohols and hydrogen halides, in the hope that more light may be throw on the mechanism of this reaction. As the formation of an alkyl halide from an alcohol and hydrogen halide is considered to be via the ions R0H2+ and (X = halogen), it is suggested that the condition of the hydrogen halide in solution is a governing factor of the mechanism. Possible mechanisms are proposed as a basis for further detailed kinetic studies.
The influence of hydrogen chloride in the thionyl chloride - alcohol system has been investigated, and it has been demonstrated that hydrogen chloride reacts readily with an alkyl sulphite according to the following equation, (R0)2S0 + 2HC1 → ROSOC1 + ROH·HC1, the extra mol. of hydrogen chloride preventing the recombination of the alkyl chlorosulphinate and alcohol.
From the interaction of hydrogen chloride (1 mol.) and (+)-tri-2-pentyl phosphite (1 mol.) there was obtained (—)-2-chloropentane with a specific rotation higher than any so far recorded. Interaction of hydrogen chloride (3 mols.) and the phosphite (1 mol.) however, gave 2-chloropentane with reduced activity together with some olefine. This reduced activity was shown to be brought about by the third dealkylation of the phosphite which indicates that the mechanism is different from the first and second dealkylation. Bromine and iodine were found to react with dialkyl hydrogen phosphites (2- and 3-pentyl), though in the case of iodine the course taken by the reaction was somewhat obscure.
An investigation has also been carried out into the decomposition of sec.-alkyl chlorosulphinates, in the presence, and in the absence of pyridine hydrochloride. The maximum yield of alkyl chloride is shown to be around 55%, due to the simultaneous formation of olefine. Possible mechanisms are suggested for both alkyl chloride formation, and olefine elimination.
Finally a procedure is described whereby neopentyl chloride can be obtained in nearly 50% yield from neopentyl chlorosulphinate, the product being free from tert.-amyl chloride.
 |
View Item |