Synthesis of Substituted 2,2’-Dinitrobiphenyls by a Novel Solvent-Free High Yielding Ullmann Coupling Biarylation:
DOI:
https://doi.org/10.31686/ijier.vol2.iss12.293

Abstract
Solvent-free reaction using a high-speed ball milling technique has been applied to the classical Ullmann coupling reaction for the first time. Biarylation of 2-iodonitrobenzene was achieved in quantitative yield when performed in a custom-made copper vial through continuous shaking without additional copper or solvent. The product was solid, NMR ready and required no lengthy extraction for purification. This reaction was cleaner, and faster than solution phase coupling which requires longer reaction time in high boiling solvents, added copper catalyst, and lengthy extraction and purification steps. Gram quantities of the biaryl compound were synthesized in larger copper vials. This is a general method that can be used to effectively reduce industrial waste en route to sustainability.
Downloads
References
a) I.P. Beletskaya, A.V. Cheprakov, Chem. Rev. 2000, 100, 3009-3066; DOI: https://doi.org/10.1021/cr9903048
b) Y. Liu, S.S. Wang, W. Liu, Q.X. Wan, H.H. Wu, G.H. Gao, Curr. Org. Chem. 2009, 13, 1322-1346; DOI: https://doi.org/10.2174/138527209789055108
c) M. Moreno-Manas, R. Pleixats, Acc. Chem. Res. 2003, 36, 638-643. DOI: https://doi.org/10.1021/ar020267y
N.T.S. Phan, M. Van Der Sluys, C.W. Jones, Adv. Synth. Catal. 2006, 348, 609-679; DOI: https://doi.org/10.1002/adsc.200505473
L.X. Yin, J. Liebscher, Chem. Rev. 2007, 107, 133-173. DOI: https://doi.org/10.1021/cr0505674
N. Miyaura, T. Yanagi, A. Suzuki, Synth. Commun. 1981, 11, 513. DOI: https://doi.org/10.1080/00397918108063618
J.K. Stille, Angew. Chem., Int. Ed. Engl. 1986, 98, 504.
E.-I. Negishi, F.-T. Luo, R. Frisbee, H. Matsushita, Heterocycles, 1982, 18, 117. DOI: https://doi.org/10.3987/S(B)-1982-01-0117
F. Ullmann, Bielecki, J. Chem. Ber. 1901, 34, 2174; DOI: https://doi.org/10.1002/cber.190103402141
F. Ullmann, Ber. Dtsch. Chem. Ges. 1904, 37, 853 – 857; DOI: https://doi.org/10.1002/cber.190403701141
I. Goldberg, Ber. Dtsch. Chem. Ges. 1906, 39, 1691 – 1696. DOI: https://doi.org/10.1002/cber.19060390298
I. P. Beletskaya and A. V. Cheprakov, Coord. Chem. Rev., 2004, 248, 2337. DOI: https://doi.org/10.1016/j.ccr.2004.09.014
A. W. Thomas and S. V. Ley, Angew. Chem. Int. Ed. 2003, 42, 5400 – 5449 DOI: https://doi.org/10.1002/anie.200300594
J. Hassan, M. Sevingnon, C. Gozzi, E. Shulz, M. Lemaire, Chem. Rev. 2002, 102, 1359 – 1469. DOI: https://doi.org/10.1021/cr000664r
P. Anastas and J. Warner, Green Chemistry: Theory and Practice, 1998.14. F. Toda, Pure Appl. Chem., 1996, 68, 285-290. DOI: https://doi.org/10.1351/pac199668020285
K. Tanaka, Solvent-Free Organic Synthesis, Wiley-VCH, Cambridge, 2003. DOI: https://doi.org/10.1002/3527601821
T.D. Nelson, R.D. Crouch, Organic Reactions Vol. 63, Chap.3, Wiley 2004.
A. de Meijere, F. Diederich, Metal-Catalyzed Cross-Coupling Reactions 2nd Ed. Vol.1 2004, Wiley-VCH DOI: https://doi.org/10.1002/9783527619535
a) K. Tanaka and F. Toda, Chem. Rev., 2000, 100, 1025-1074. DOI: https://doi.org/10.1021/cr940089p
b) Y.-W. Dong, G.-W. Wang and L. Wang, Tetrahedron, 2008, 64, 10148-10154. DOI: https://doi.org/10.1016/j.tet.2008.08.047
a) D. C. Waddell and J. Mack, Green Chem., 2009, 11, 79-82. DOI: https://doi.org/10.1039/B810714A
b) D. C. Waddell, I. Thiel, T. D. Clark, S. T. Marcum and J. Mack, Green Chem., 2010, 12, 209-211. DOI: https://doi.org/10.1039/B922108P
c) J. Mack, D. Fulmer, S. Stofel and N. Santos, Green. Chem., 2007, 9, 1041-1043. DOI: https://doi.org/10.1039/b706167f
Gregor, R.W.; Goj, L.A., J.Chem.Ed. 2011, 88, 331-333. DOI: https://doi.org/10.1021/ed900024u
A.K. Epps, G.R. Mandouma, manuscript submitted for publication.
J. Forrest, J. Chem. Soc, 1960, 592. DOI: https://doi.org/10.1039/jr9600000592
N. Kornblum, D.L. Kendall, J. Am. Chem. Soc. 1952, 74, 5782. DOI: https://doi.org/10.1021/ja01142a518
A. Concas, N. Lai, M. Pisu, G. Cao, Chem. Eng. Sci., 2006, 61, 3746-3760. 25. a) W.S. Rapson, RG Shuttleworth, Nature, 1941, 147, 675; DOI: https://doi.org/10.1016/j.ces.2006.01.007
b) F. Bell, W.H.D. Morgan, J. Chem. Soc, 1954, 1716 DOI: https://doi.org/10.1039/JR9540001716
a) G.O. Jones, P. Liu, K.N. Houk, S.L. Buchwald, J Am Chem Soc. 2010, 132, 6205–6213; DOI: https://doi.org/10.1021/ja100739h
b) E. Sperotto, G.P.M. van Klink, G. van Koten, J.G. de Vries, Dalton Trans., 2010, 39, 10338–10351 DOI: https://doi.org/10.1039/c0dt00674b
Downloads
Published
Issue
Section
License
Copyright (c) 2014 Ghislain R Mandouma, Ayunna Epps, John Barbas

This work is licensed under a Creative Commons Attribution-NoDerivatives 4.0 International License.
Copyrights for articles published in IJIER journals are retained by the authors, with first publication rights granted to the journal. The journal/publisher is not responsible for subsequent uses of the work. It is the author's responsibility to bring an infringement action if so desired by the author for more visit Copyright & License.