Hexamethylene chlorohydrin

Sodium hydroxide should not be substituted here because of the lower solubility of the sodium salt. 

The alkali-insoluble material (3-9 g.) can be washed with water, dried, and recrystallized from 95% ethanol to yield from 1 to 5 g. of pure 2-acetylfluorenone melting at 154-155°. Alternatively, it can be added to the next lot of 2-acetylfluorene if another oxidation is to be carried out. 

This melting point corresponds to that given in the literature. - The submitters report that the product can be recrys-taUized from acetic anhydride or Cellosolve. 

The method described is a modification of the method of Dzie-wonski and Schnayder and is described in a patent by the submitters. Fluorenone-2-carboxylic acid has also been obtained by the oxidation of 2-fluorenealdehyde.  

1 Dziewonski and Schnayder, Bull, intern, acad. polon. sci., 1930A, 529 [C.A., 25, 5416 (1931)]. 

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In the original work of Bennett and Turner a petroleum fraction of b.p. 90-120° was used. When the submitters used Skellysolve L, b.p. 90-100°, the hexamethylene chlorohydrin was not sufficiently soluble in it to be removed from the reaction mixture. A study of the solubility of hexamethylene chlorohydrin in various commonly available solvents was made, and toluene was found to be the most satisfactory. 

Hexamethylene chlorohydrin has been prepared by the reaction of hydrochloric acid with hexamethylene glycol, without a catalyst or in the presence of cuprous chloride. ... 

Ethylene oxide was conventionally prepared by reacting CI2, ethylene, and water to produce chlorohydrin, which is further treated with caustic to generate the oxide. This process was superseded by the direct oxidation of ethylene in the presence of silver catalysts with air or oxygen. The isobutane process displaced the route fiom propylene chlorohydrin to produce PO. Another significant loss was the conversion of DuPont s hexamethylene diamine process from butadiene to a non-chlorine-based technology. All these changes led to a loss of 140 000 tons of market demand for chlorine. 

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