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Supplementary Material (ESI) for Green Chemistry This journal is ? The Royal Society of Chemistry

2008 S1 Silica-assisted Suzuki-Miyaura reactions of heteroaryl bromides in aqueous media Shengyin Shi, Yuhong Zhang? Department of Chemistry, Zhejiang University, Hangzhou 310027, P.

R. China. E-mail: yhzhang@ zju.edu.cn Supporting Information Content General procedure for Suzuki-Miyaura reaction…S2 Characterization data of the products of Suzuki-Miyaura reaction………S4 References…S41 Supplementary Material (ESI) for Green Chemistry This journal is ? The Royal Society of Chemistry

2008 S2 General All the starting materials and solvents were purchased from common commercial sources and were used without additional purification. The gas chromatography analysis was performed on a GC instrument.

1 H NMR spectra were recorded at

500 MHz or

400 MHz using TMS as internal standard.

13 C NMR spectra were recorded at

125 MHz using TMS as internal standard. Mass spectroscopy data of the product was collected on a MS-EI instrument. The transmission electron micrographs (TEM) and selected area electron diffraction (SAED) patterns were obtained by employing JEM-2010 microscopes under

200 kV. Samples for observation of TEM were prepared by placing CH3OH solution of reaction remnant onto a carbon-coated copper grid. Except T3-13 and T3-14, which were new compounds and thoroughly characterized by

1 H NMR,

13 C NMR, MS, and HRMS, the other prepared compounds are known and the analysis of

1 H NMR as well as MS for them is performed. In addition, the CA numbers as well as the related preparation and characterization references are presented in this supporting information. General procedure for the Suzuki-Miyaura reaction: A mixture of NaOH (0.80 g,

2 mmol) or Na2CO3 (0.216 g, 2mmol), Pd(OAc)2 (1 mg, 0.5 mol%), silica gel (10-40 μm) (0.2 g), aryl bromide (1 mmol), arylboronic acid (1.5 mmol), distilled water (3 mL) and PEG

2000 (3.5 g) was stirred at

80 o C for the indicated time. Afterward, the reaction solution was cooled to room temperature and extracted four times with diethyl ether (4*15 mL). GC and GC/MS analyzed the combined organic Supplementary Material (ESI) for Green Chemistry This journal is ? The Royal Society of Chemistry

2008 S3 phase. The further purification of the product was achieved by flash chromatography on a silica gel column. In the recycling experiment, the residue was subjected to a second run of the Suzuki reaction by charging it with the same substrates (3-bromopyridine, phenylboronic acid, NaOH) without further addition of Pd(OAc)2 or PEG

2000 or silica gel. In the third, fifth, seventh, ninth and eleventh run, 0.5 ml distilled water was added to the reaction mixture. In the thirteenth, fifteenth and seventeenth run, 1.0 ml distilled water was added to the reaction mixture. Supplementary Material (ESI) for Green Chemistry This journal is ? The Royal Society of Chemistry

2008 S4 Characterization data of the products of Suzuki-Miyaura reaction

1、 N 3-Phenyl-pyridine [T2-1, 1008-88-4, Ref. 1]

1 H NMR (400 MHz, CDCl3, TMS) δ 8.83 (d,

1 H, J = 1.2 Hz), 8.55-8.56 (m,

1 H), 7.80-7.83 (m,

1 H), 7.53-7.55 (m,

2 H), 7.42-7.45 (m,

2 H), 7.29-7.38 (m,

2 H). MS (EI): m/z (%):

155 (100) [M+ ],

154 (22),

153 (15),

76 (9) Supplementary Material (ESI) for Green Chemistry This journal is ? The Royal Society of Chemistry

2008 S5

2、 N Cl 2-chloro-3-phenylpyridine [T2-2, 31557-57-0, Ref. 2]

1 H NMR (400 MHz, CDCl3, TMS) δ 8.39 (dd,