Summary
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1.
The catalytic vapor-phase dehydration of pinacol has a stagewise character. In the first stage the process proceeds in two directions: with formation of pinacolone and with formation of dimethylbutenol. The complete dehydration of pinacol gives 2,3-dimethy 1−1,3-butadiene.
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2.
The two acid-catalyzed reactions, the pinacol-pinacolone rearrangement and the dehydration of pinacol, are accelerated to different extents by different catalyst having acidic properties. Silica gel, aluminum silicate, and borophosphate (at 300°) catalyze the process preferentially in the direction of the pinacolone rearrangement. In presence of calcium phosphate at 300° and above the main reaction product is dimethylbutadiene, which is probably formed via the stage of the formation of the unsaturated alcohol dimethylbutenol. It is probable that in presence of alumina the diene may be formed through the intermediate formation both of the unsaturated alcohol and of pinacolone.
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Freidlin, L.K., Sharf, V.Z. Two directions of the catalytic vapor-phase dehydration of pinacol. Russ Chem Bull 11, 646–649 (1962). https://doi.org/10.1007/BF00904769
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DOI: https://doi.org/10.1007/BF00904769