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An Efficient Synthesis of 1,2,3-triazole Bridge-connected Phosphonate
Derivatives of Coumarin
Xu Li,1 Xiaolan Chen,1 Jinwei Yuan,2 Yang Liu,1 Peipei Li,1 Lingbo Qu,1,2* and Yufen
Zhao1,3
1
Department of Chemistry, Zhengzhou University, Key Laboratory of Organic Chemistry and
Chemical Biology, Henan Province, Zhengzhou, 450052, P. R. China
2
Chemistry and Chemical Engineering School, Henan University of Technology, Henan
Province, Zhengzhou 450001, P. R. China
3
Department of Chemistry, Xiamen University, Xiamen, 361005, P. R. China
Email: chenxl@zzu.edu.cn
Supplemental Materials
Preparation of diethyl 2-bromoethylphosphonate (1)
1,2-dibromoethane (150 mL, 1.75 mol) was placed into a 250 mL three-necked flask, and the
solution was slowly heated to 160 C with vigorous stirring. Triethyl phosphite (60 mL, 0.35
mol) was added dropwise over the course of 1 h, and the reaction was monitored by 31P NMR
spectrum. When the peak at δ 137 ppm disappeared, the reaction was finished. The solution was
cooled to room temperature and distilled at reduced pressure (1-5 mbar at 110-128 C, ref.1 105130 C) to give colourless oil 1 (59.8 g, 70.0%). 1H NMR (CDCl3)  = 4.12 (m, 4H), 3.54 (m,
2H), 2.39 (m, 2H), 1.34 (t, J = 14.4 Hz, 1H). 13C NMR (CDCl3)  = 65.6, 48.2 (d, J =10.0 Hz),
29.3 (d, J = 140.0 Hz), 19.2. 31P NMR (CDCl3)  = 25.1.
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Preparation of diethyl 2-azidoethylphosphonate (2)
A solution of sodium azide (1.3 g, 20.0 mmol) in water (5.0 mL) was added to a vigorously
stirred solution of diethyl 2-bromoethyl phosphonate (2.4 g, 10.0 mmol) in DMF (20 mL) at
room temperature. The mixture solution was stirred over 48 h at room temperature. The reaction
course was monitored by 31P NMR. The reaction was finished, and the solution was extracted
with dichloromethane (30 mL × 3), and the combined organic phase was dried over Na2SO4. The
solvent was removed in vacuo and the crude product was purified by flash column
chromatography on silica gel using EtOAc:hexane (1:1) as the eluent to afford the colorless oil 2
(1.9 g, 92%). IR (KBr) ν (cm−1) = 2103, 1248, 1028, 965. 1H NMR(CDCl3)  = 1.32 (t, J = 7.1
Hz, 6H, CH3), 2.04 (dt, J = 18.6 Hz, J = 7.7 Hz, 2H, PCH2), 3.52 (dt, J = 7.8 Hz, J = 7.7 Hz, 2H,
NCH2), 4.07-4.11 (m, 4H, OCH2). 13C NMR (CDCl3)  = 61.7, 45.1 (d, J = 10.0 Hz), 26.4 (d, J =
140.0 Hz), 16.2. ESI MS: m/z = 208.0 [M + H]+. Spectroscopic data was in accordance with that
reported literature.2
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Figure S 1 1H NMR spectrum of compound 5a
Figure S 2 13C NMR spectrum of compound 5a
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Figure S 3 31P NMR spectrum of compound 5a
Figure S 4 1H NMR spectrum of compound 5b
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Figure S 5 13C NMR spectrum of compound 5b
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31P
Figure S 6
NMR spectrum of compound 5b
Figure S 7 1H NMR spectrum of compound 5c
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Figure S 8 13C NMR spectrum of compound 5c
Figure S 9 31P NMR spectrum of compound 5c
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Figure S 10 1H NMR spectrum of compound 5d
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Figure S 11 13C NMR spectrum of compound 5d
Figure S 12 31P NMR spectrum of compound 5d
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Figure S 13 1H NMR spectrum of compound 5e
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Figure S 14 13C NMR spectrum of compound 5e
Figure S 15 31P NMR spectrum of compound 5e
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Figure S 16 1H NMR spectrum of compound 5f
Figure S 17 13C NMR spectrum of compound 5f
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Figure S 18 31P NMR spectrum of compound 5f
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Figure S 19 1H NMR spectrum of compound 5g
Figure S 20 13C NMR spectrum of compound 5g
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Figure S 21 31P NMR spectrum of compound 5g
Reference：
1.
Cichowicz, N. R.; Nagorny, P. Org. Lett. 2012, 14, 1058-1061.
2.
Yang, S. H.; Lee, D. J.; Brimble, M. A. Org. Lett. 2011, 13, 5604-5607.