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Blanc chloromethylation

  • Page ID
    66869
  • The Blanc chloromethylation (also called the Blanc reaction) is the chemical reaction of aromatic rings with formaldehyde and hydrogen chloride catalyzed by zinc chloride or other Lewis acid to form chloromethyl arenes. The reaction was discovered by Gustave Louis Blanc (1872-1927) in 1923. The reaction is performed with care as, like most chloromethylation reactions, it produces highly carcinogenic bis(chloromethyl) ether as a by-product.

    The Blanc chloromethylation

    Mechanism

    The reaction is carried out under acidic conditions and with a ZnCl2 catalyst. These conditions protonate the formaldehyde carbonyl making the carbon much more electrophilic. The aldehyde is then attacked by the aromatic pi-electrons, followed by rearomatization of the aromatic ring. The benzyl alcohol thus formed is quickly converted to the chloride under the reaction conditions.

    Mechanism of Blanc chloromethylation

    Although the reaction is an efficient means of introducing a chloromethyl group, the production of small amounts of highly carcinogenic bis(chloromethyl) ether is a disadvantage.

    Related chloromethylations

    Chloromethylation can also be effected using chloromethyl methyl ether:

    ArH + CH3OCH2Cl → ArCH2Cl + CH3OH

    This reaction is employed in the chloromethylation of styrene in the production of ion-exchange resins and Merrifield resins.