Kinetic studies have been made of the titanium tetrachloride catalyzed reactions between benzyl chloride and benzene or toluene in an excess of the aromatic hydrocarbon at 30 °C. The reaction follows first-order dependence upon benzyl chloride and is second order with respect to catalyst. The results depend strongly on the amount of moisture present. Where moisture is minimized using new vacuum line procedures, the results obtained, kT/kB = 20 (±12) and isomer product distribution 41 (±3)% ortho, 6 (±2)% meta, and 53 (±3)% para methyldiphenylmethane, are in good agreement with Brown's selectivity relationship. The reaction mechanism is discussed in terms of attack by a benzyl cation or an ion pair [C6H6CH2+ Ti2Cl9_] on the aromatic.
Recently reported benzylation results in excess aromatic hydrocarbon and in nitromethane indicate the reaction to be moderate in rate and free of undesirable isomerization and disproportionation side reactions.1 Benzylation therefore is not subject to the sort of criticism raised concerning the validity of data for fast competitive reactions (nitration2 and haloge-nation3), where mixing rates may be slow compared with the rate of reaction. Thus, the relatively slow benzylation reaction
Die Titelreaktion, die in Gegenwart des milden Katalysators TiCl4 mit Benzylchlorid durchgeführt wird und im überschüssigen Toluol feuchtigkeitsempfindlich ist, führt zu einem Isomerenverhältnis o : m : p = 41 26: 53 (bzw. 45 : 6:49 in Nitromethan).
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