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The Royal Society of Chemistry"

Arene bromomethylation

SyntheticPage 423

Submitted: June 1, 2010, published: June 1, 2010

Authors

Suzanne Elizabeth Howson (s.e.howson@warwick.ac.uk)

A contribution from 

Reaction Scheme

Chemicals

Diphenylmethane
HBr (48% aq.)
Acetic Acid (glacial)
1,3,5-Trioxane
Tetradecyltrimethylammonium Bromide

Procedure

Diphenylmethane (5.00 g, 29.72 mmol, 1.0 eq.) was added to a solution of 48% aq. HBr (80 ml) and glacial acetic acid (21 ml). 1,3,5-trioxane (5.35 g, 59.44 mmol, 2.0 eq.) was then added to the mixture, followed by tetradecyltrimethylammonium bromide (0.16 g, 0.48 mmol, 0.016 eq.). The reaction was stirred at reflux (125°C) overnight (16 h). After this time the solution was cooled to ambient temperature, then to 0°C in an ice-water bath. The dark yellow solid was filtered off and washed with several portions of water. The solid was then dissolved in DCM (150 ml), washed with water (100 ml) before drying the DCM layer over Na2SO4. This was filtered and the solvent removed in vacuo leaving a light yellow solid, which was recrystallised from hot DCM leaving the pure product as a white solid. Yield = 2.63 g, 7.43 mmol, 25%.

Author Comments

Reaction also successfully carried out replacing diphenylmethane with bibenzyl.

Data

1H NMR (400 MHz, 298 K, CDCl3) 7.32 (4H, d, 3JHH = 8 Hz, Ph), 7.15 (4H, d, 3JHH = 8 Hz, Ph), 4.48 (4H, s, CH2Br), 3.96 (2H, s, CH2).


13C{1H} NMR (100 MHz, 298 K, CDCl3) 141.1 (Ph), 135.7 (Ph), 129.3 (Ph), 129.2 (Ph), 41.3 (CH2), 33.4 (CH2Br).

Lead Reference

R. H. Mitchell and V. S. Iyer, Synlett, 1989, 55-57 (General procedure for bromomethylation in the para position on a phenyl ring)

Supplementary Information

Keywords

addition, alkyl/alkenyl/aryl halides, aromatics/arenes, bromomethylation