Efficient Synthesis of Bis(dibromomethyl)arenes as Important Precursors of Synthetically Useful Dialdehydes

Abstract

This work presents an efficient synthesis of bis(dibromomethyl)benzenes and a bis(dibromomethyl)thiophene as precursors of aromatic dialdehydes by bromination of dimethyl-substituted arenes under various reaction conditions (yields up to 99%). Several new variants of this reaction, including the use of N-bromosuccinimide (NBS) and bromine, and various solvents to replace carbon tetrachloride, benzene and carbon disulfide, were also tested. In the optimised protocols, the inconvenient solvents were replaced by 1,2-dichloroethane (DCE) and/or acetonitrile. In the DCE protocols, we reduced reaction times 24–32-fold, reduced the amount of NBS a fewfold and lowered power consumption relative to the literature protocols. The procedures also allowed elimination of long-lasting incandescent irradiation (100–500 W). The replacement of NBS by bromine led to a further reduction in the amount of brominating agent. The obtained bromo derivatives were efficiently converted into the corresponding dialdehydes (90–96%), which in turn are useful in materials chemistry.

Key words

bis(dibromination) - dialdehydes - radical reaction - solvents - bromine - N-bromosuccinimide

• References

• 1a Bonifacio MC, Robertson CR, Jung J.-K, King BT. J. Org. Chem. 2005; 70: 8522
• 1b Yang X, Liu D, Miao Q. Angew. Chem. Int. Ed. 2014; 53: 6786
• 1c Toyoshima T, Yoshida S, Watanabe S. Tetrahedron 2013; 69: 1904
• 1d Buu-Hoi NP, Nguyen D.-X, Nguyen V.-B. Proc. Int. Conf. Methods Prep. Stor. Label. Compounds 1968; 215
• 2 Lin S.-H, Wu F.-I, Liu R.-S. Chem. Commun. 2009; 45: 6961
• 3 Shen P, Sang G, Lu J, Zhao B, Wan M, Zou Y, Li Y, Tan S. Macromolecules 2008; 41: 5716
• 4 Shi Z, Zhang X, Yang G, Su Z, Cui Z. Tetrahedron 2011; 67: 4110
• 5 Zhang X, Li M, Shi Z, Zhao L, Jin R, Yi M, Zhang D, Cui Z. Dyes Pigm. 2012; 92: 982
• 6 Neo WT, Cho CM, Song J, Chin JM, Wang X, He C, Chan HS. O, Xu J. Eur. Polym. J. 2013; 49: 2446
• 7a Bałczewski P, Skalik J, Uznański P, Guziejewski D, Ciesielski W. RSC Adv. 2015; 5: 24700
• 7b Bałczewski P, Bodzioch A, Skalik J, Koprowski M. EPO Appl. No EP 121877088, 2012
• 8 Tietze LF, Krahnert W.-R. Chem. Eur. J. 2002; 8: 2116
• 9 Harvey RG, Dai Q, Ran C, Penning TM. J. Org. Chem. 2004; 69: 2024
• 10 Zhang Y, Song G, Ma G, Zhao J, Pan C.-L, Li X. Organometallics 2009; 28: 3233
• 11 Alfonsi K, Colberg J, Dunn PJ, Fevig T, Jennings S, Johnson TA, Kleine HP, Knight C, Nagy MA, Perry DA, Stefaniak M. Green Chem. 2008; 10: 31
• 12 Levine DR, Caruso AJr, Siegler MA, Tovar JD. Chem. Commun. 2012; 48: 6256
• 13a Amijs CH. M, van Klink GP. M, van Koten G. Green. Chem. 2003; 5: 470
• 13b Mestres R, Palenzuela J. Green Chem. 2002; 4: 314
• 13c Offermann W, Vögtle F. Synthesis 1977; 272
• 14 Liu Z, Yasseri AA, Loewe RS, Lysenko AB, Malinovskii VL, Zhao Q, Surthi S, Li Q, Misra V, Lindsey JS, Bocian DF. J. Org. Chem. 2004; 69: 5568
• 15 Frey J, Bond AD, Holmes AB. Chem. Commun. 2002; 2424
• 16 Sheldrick GM. Acta Crystallogr., Sect. A 2008; 64: 112