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Blanc chloromethylation

Lianyungang Klinechem Co.,Ltd | Updated: Nov 30, 2018

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.

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

Related chloromethylations

Chloromethylation of thiols can be effected with concentrated HCl and formaldehyde:[4]

  • ArSH + CH2O + HCl → ArSCH2Cl + H2O

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.[5]

See also

  • Friedel-Crafts alkylation

  • Quelet reaction

  • Bouveault–Blanc reduction

References

  1. ^ Gustave Louis Blanc Bull. Soc. Chim. France 192333, 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 Chemistry38 (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 Reviews46 (9): 891–903. Bibcode:1977RuCRv..46..891B. doi:10.1070/RC1977v046n09ABEH002180.

  4. ^ D. Enders, S. Von Berg, B. Jandeleit (2002). "Diethyl [(Phenylsulfonyl)methyl]phosphonate". Org. Synth78: 169. doi:10.15227/orgsyn.078.0169.

  5. ^ 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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