Synthesis 2016; 48(20): 3509-3514
DOI: 10.1055/s-0035-1561651
paper
© Georg Thieme Verlag Stuttgart · New York

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

Agnieszka Bodzioch*
a  Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland
,
Krzysztof Owsianik
a  Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland
,
Joanna Skalik
a  Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland
,
Emilia Kowalska
a  Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland
,
Anna Stasiak
a  Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland
,
Ewa Różycka-Sokołowska
b  Jan Długosz University in Częstochowa, Institute of Chemistry, Environmental Protection and Biotechnology, The Faculty of Mathematics and Natural Sciences, Armii Krajowej 13/15, 42-201 Częstochowa, Poland   Email: agabodz@interia.pl   Email: pbalczew@cbmm.lodz.pl
,
Bernard Marciniak
b  Jan Długosz University in Częstochowa, Institute of Chemistry, Environmental Protection and Biotechnology, The Faculty of Mathematics and Natural Sciences, Armii Krajowej 13/15, 42-201 Częstochowa, Poland   Email: agabodz@interia.pl   Email: pbalczew@cbmm.lodz.pl
,
Piotr Bałczewski*
a  Department of Heteroorganic Chemistry, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland
b  Jan Długosz University in Częstochowa, Institute of Chemistry, Environmental Protection and Biotechnology, The Faculty of Mathematics and Natural Sciences, Armii Krajowej 13/15, 42-201 Częstochowa, Poland   Email: agabodz@interia.pl   Email: pbalczew@cbmm.lodz.pl
› Author Affiliations
Further Information

Publication History

Received: 15 April 2016

Accepted after revision: 27 April 2016

Publication Date:
09 June 2016 (online)


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.

Supporting Information

 
  • 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