Studies on Chlorination of Neopentyl-Type Polyols with Gaseous Hydrogen Chloride.I:Chlorination of Pentaerythritol

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Though primary alcohols are, in general, readily chlorinated with hydrogen chloride, neopentyl-type polyols such as pentaerythr.itol undergo chlorination with difficulty. Upon addition of a small amount of acetic acid, however, chlorination reaction is effected with ease. In order to clarify the catalytic mechanism of acetic acid, the chlorination of pentaerythritol and pentaerythritol dichlorohydrin has been studied. Though in the absence of acetic acid, pentaerythritol dichlorohydrin failed to react with hydrogen chloride, pentaerythritol trichloride was formed quantitatively when a proper amount of acetic acid was added. The true reactant, in this case, was found to be pentaerythritol dichloromonoacetatemonohydrin. Under the constant flow of hydrogen chloride gas, the reaction velocity was poportional to the first order of the true reactant concentration. In the presence of a proper amount of acetic acid, pentaerythritol was converted to the mono-, di-, or tri-chlorinated products with relatively good selectivity under given conditions.Dipentaerythritol tetrachlorodiacetate has been isolated as a by-product from the chlorinated product mixtures.
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