1,2,4,5-TETRAKIS(BROMOMETHYL)BENZENE

Chemical Properties

off-white to light yellow crystalline powder

Uses

1,2,4,5-Tetrakis(bromomethyl)benzene has been used in the synthesis of:

• tetrapodal imidazolium ligands as their PF₆ salts
• 6,7-bis(bromomethyl)-2,11,18,21,24-pentaoxatetracyclo[23.4. 0.0^4,9.0¹²,¹⁷]nonacosa-1(25),4(9),5,7,12 (17),13,15,26,28-nonaene
• conformationally constrained cyclic α-amino acid derivatives
• thiacyclophanes
• dendrimeric organoplatinum complexes

Synthesis

95-93-2

15442-91-8

General procedure for the synthesis of tetrabromotoluene from 1,2,4,5-tetramethylbenzene: 1,2,4,5-tetrakis(bromomethyl)benzene (2.8 g, 20 mmol) was prepared by reacting 1,2,4,5-tetramethylbenzene (2.8 g, 20 mmol) with N-bromosuccinimide (NBS, 14.4 g, 80 mmol) and benzoyl peroxide in 50 mL of tetrachloromethane (1c, 1 g, 5.9 mmol). The reaction mixture was heated at 77 °C for 50 min. After completion of the reaction, the precipitate was collected by filtration under reduced pressure and washed with hot tetrachloromethane. The filtrate was concentrated to a small volume and cooled to 4 °C. The crude product was filtered and purified by recrystallization from methanol. The reaction time was less than 1 hour to give a white solid product in 15% yield with a melting point of 159-160°C. The structure of the product was determined by 1H-NMR (CDCl3, δ: 7.37 ppm, 2H, a; 4.60 ppm, 8H, b), 13C-NMR (CDCl3, δ: 137.6 ppm, a; 133.6 ppm, h; 28.7 ppm, b), and FT-IR (KBr, νmax: 3026, 2980, 2933. 1504, 1456, 1210, 911, 797, 678, 598 cm-1) were characterized.

References

[1] Journal of the Chinese Chemical Society, 2002, vol. 49, # 1, p. 77 - 82
[2] Angewandte Chemie - International Edition, 2006, vol. 45, # 26, p. 4281 - 4286
[3] Molecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals, 1994, vol. 247, p. 23 - 30
[4] Heterocycles, 2015, vol. 90, # 1, p. 645 - 658
[5] Tetrahedron Letters, 2015, vol. 56, # 26, p. 3992 - 3995