Supporting information

Synthesis of aryl azides from aryl halides promoted by Cu2O/tetraethylammonium prolinate

Abdol Reza Hajipour* a,b and Fatemeh Mohammadsalehb

a Department of Pharmacology, University of Wisconsin, Medical School, 1300 University Avenue, Madison, 53706-1532 WI,

USA

b Pharmaceutical Research Laboratory, Department of Chemistry, Isfahan University of Technology, Isfahan 84156, Islamic

Republic of Iran

*Corresponding author. Tel: +98-311-391-3262; Fax: +98-311-391-2351E-mail address: haji@cc.iut.ac.ir

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General procedure for synthesis of Cu2O particles:

1g of polyvinyl alcohol (crystalline powder, high molecular weight) was dissolved in 50 ml

distilled water. In another beaker, a solution of NaOH (4.0 g) in 25 ml distilled water was

prepared and this solution was added to the PVA solution under stirring; and then, the mixture

was heated at 70 ˚C for 3 h. After cooling, the solution of CuSO4.5H2O (1.25 g) in 20 ml distilled

water was added dropwise to the above PVA solution under vigorous stirring. A green gel was

produced when CuSO4 solution was added and the mixture was heated at 90 ˚C for 4 h. After

cooling the reaction mixture, ascorbic acid solution (0.89 g in 10 mL distilled water) was added

dropwise into the PVA–Cu(II) reaction mixture at room temperature under very rapid stirring.

After several seconds, the orange-red particles appeared in the reaction mixture. The resulting

mixture was then aged in air at room temperature, overnight. A reddish product obtained which

was then washed with distilled water and ethanol several times to remove impurities and dried in

air.

X-ray powder diffraction (XRD) and Scanning Electron Microscopy (SEM) analysis were used

to characterize the as-prepared Cu2O particles. The XRD pattern (Figure 1) indicates diffractions

of Cu2O particles, containing six peaks that are clearly distinguishable and all of them can be

perfectly indexed to crystalline Cu2O particles. The peak positions are in good agreement with

those for Cu2O powder reported in references (JCPDS 5-667).1

Figure 1. XRD patterns of as-prepared Cu2O particles

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The SEM images were taken with a Hitachi S-4160 Field Emission Scanning Electron

Microscopy (FESEM). The images in Figure 2 clearly manifest the Cu2O crystals with the

different diameters.

Figure 2. SEM images of synthesized Cu2O particles

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HNMR and FTIR date:

The aryl azide products are known compounds and their literature references have been provided.2-5

1-Azido-4-iodobenzene: yellow solid2, mp. 40 oC

FTIR (KBr film, cm-1): 2125, 2090.1H NMR (500 MHz, CDCl3) δ 7.67 (d, 2H), 6.82 (d, 2H).

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1-Azido-4-methoxybenzene: yellow oil3

FTIR (KBr film, cm-1): 2105.

1-Azido-3-nitrobenzene: yellow solid3, mp. 58-59 oC

FTIR (KBr film, cm-1): 2124, 2104.

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4-Azidophenol: reddish black oil4

FTIR (KBr film, cm-1): 2112, 2072.

1-Azido-4-methylbenzene: yellow oil3

FTIR (KBr film, cm-1): 2137, 2103.

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4-Azidoaniline: dark brown oil5

FTIR (KBr film, cm-1): 2111, 2075.

References

1. Joint Committee on Powder Diffraction Standards, Diffraction Data File, No. 5-667,

ICDD International Center for Diffraction Data (formerly JCPDS), Pennsylvania, USA

1991.

2. Sandler, S. R., Karo, W. Orgnic Functional Group Preparations, Vol. II. Academic

Press, London, 1971, p.266.

3. eKutonova, AK..V., Trusova, M. E., Postnikov, P. S., Filimonov, V. D., Parello, J.

Synthesis 2013, 45, 2706–2710.

4. Fotea, C., D’Silva, C. Int. J. Adhes. Adhes. 2005, 25, 442-449.

5. Grimes, K. D., Gupte, A., Aldrich, C. C. Synthesis 2010, 1, 1441–1448.

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