Blanc chloromethylation

Blanc chloromethylation
Named after Gustave Louis Blanc
Reaction type Substitution reaction
Identifiers
Organic Chemistry Portal blanc-reaction

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.[1][2][3] The reaction is performed with care as, like most chloromethylation reactions, it produces highly carcinogenic bis(chloromethyl) ether as a by-product.

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.

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.[4]

See also

References

  1. ↑ Gustave Louis Blanc Bull. Soc. Chim. France 1923, 33, 313
  2. ↑ Whitmore, F. C.; Ginsburg, Abram; Rueggeberg, Walter; Tharp, I.; Nottorf, H.; Cannon, M.; Carnahan, F.; Cryder, D.; FLeming, G.; Goldberg, G.; Haggard, H.; Herr, C.; Hoover, T.; Lovell, H.; Mraz, R.; Noll, C.; Oakwood, T.; Patterson, H.; Van Strien, R.; Walter, R.; Zook, H.; Wagner, R.; Weisgerber, C.; Wilkins, J. (May 1946). "Production of Benzyl Chloride by Chloromethylation of Benzene. Laboratory and Pilot Plant Studies". Industrial & Engineering Chemistry. 38 (5): 478–485. doi:10.1021/ie50437a013.
  3. ↑ Belen'kii, Leonid I; Vol'kenshtein, Yu B; Karmanova, I B (30 September 1977). "New Data on the Chloromethylation of Aromatic and Heteroaromatic Compounds". Russian Chemical Reviews. 46 (9): 891–903. doi:10.1070/RC1977v046n09ABEH002180.
  4. ↑ François Dardel and Thomas V. Arden "Ion Exchangers" in Ullmann's Encyclopedia of Industrial Chemistry, 2008, Wiley-VCH, Weinheim. doi:10.1002/14356007.a14_393.pub2
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