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2-methoxy diaryl ether (2a):
1
Yield 78%; H NMR (CDCl3, 500MHz) ꢀ (ppm) 3.91(s,
3H), 6.97-7.19(m, 6H), 7.16(t, 1H, J 10.5 Hz), 7.33(t, 2H, J
11.0 Hz).
[8]
[9]
4-methoxy diaryl ether (2b):
1
Yield 74%; H NMR (CDCl3, 500MHz) ꢀ (ppm) 3.84(s,
3H), 6.92(dd, 2H, J1 3.5 and J2 8.5 Hz), 6.98(dd, 2H, J1 2.0
and J2 10.5 Hz), 7.03(dd, 2H, J1 4.0 and J2 8.5 Hz), 7.09(t,
1H, J 10.5 Hz), 7.32(dd, 2H, J1 3.5 and J2 12.0 Hz).
[10]
[11]
4. CONCLUSION
In the present study, we obtained an efficient and sample
route to synthesis of diaryl ethers. Meanwhile, the structural
parameters of four types of aryl halides and ionization en-
ergy of four types of aryl halides were calculated by
Gaussian 03 program. Relationship between structural pa-
rameters and reactivity of four types of aryl halides was dis-
cussed. In addition, the ionization energy order of the four
kinds of aryl halides is: fluorobenzene >> chlorobenzene >
bromobenzene > iodobenzene, which indicates that the Ull-
man reactivity of iodobenzene is the biggest, and Ullman
reactivity of fluorobenzene is the lowest. This result corre-
sponds to Ullman reaction conversions that were determined
by HPLC. Theoretical investigations of the reactivity of aryl
halides would provide useful working guidelines for the de-
sign of reaction system. Besides, under the optimum reaction
condition two kinds of methoxy substituted diaryl ethers
were synthesized, which means the optimum reaction condi-
tions obtained have certain applicability.
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CONFLICT OF INTEREST
The authors confirm that this article content has no con-
flicts of interest.
[16]
[17]
[18]
[19]
ACKNOWLEDGEMENTS
Niu J.J.; Zhou, H.; Li, Z.G.; Xu, J.W.; Hu, S.J. An efficient Ull-
mann-Type CꢀO bond formation catalyzed by an air-stable cop-
per(I)ꢀbipyridyl complex. J. Org. Chem., 2008, 73, 7814-7817.
Armelle, O.; Jean, F.S.; Henri, J.C.; Marc, T. Mild conditions for
copper-catalyzed coupling reaction of phenols and aryl iodides and
bromides. Adv. Synth. Catal., 2006, 348, 499-505.
This research was financially supported by the National
Natural Science Foundation of China (No. 41071319,
20977046 and 20737001), the National Basic Research Pro-
gram of China (2009CB42160-4), the Fundamental Research
Funds for the Central Universities of China (No.
1112021101) and the Major Science and Technology Pro-
gram for Water Pollution Control and Treatment of China
(No. 2012ZX07506-001).
Frisch, M.J.; Trucks, G.W.; Schlegel, H.B.; Scuseria, G.E.; Robb,
M.A.; Cheeseman, J.R.; Zakrzewski, V.G.; Montgomery, J.A.;
Stratmann, R.E.; Burant, J.C.; Dapprich, S.; Millam, J.M.; Daniels,
A.D.; Kudin, K.N.; Strain, M.C.; Farkas, O.; Tomasi, J.; Barone,
V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.;
Clifford, S.; Ochterski, J.; Petersson, G.A.; Ayala, P.Y.; Cui, Q.;
Morokuma, K.; Malick, D.K.; Rabuck, A.D.; Raghavachari, K.;
Foresman, J.B.; Cioslowski, J.; Ortiz, J.V.; Baboul, A.G.; Stefanov,
B.B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts,
R.; Martin, R.L.; Fox, D.J.; Keith, T.; Al-Laham, M.A.; Peng,
C.Y.; Nanayakkara, A.; Challacombe, M.; Gill, P.M.W.; Johnson,
B.; Chen, W.; Wong, M.W.; Andres, J. L.; Gonzalez, C.; Head-
Gordon, M.; Replogle, E.S.; Pople, J.A. Gaussian 03, Revision A.1,
Gaussian, Inc, Pittsburgh, PA. 2003.
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