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Synthesis of Novel Phosphorylated Chrysin Derivatives
by 1, 3-Dipolar Cycloaddition Reaction
Shaohua Zhu,1 Yan Zhang,1 Peipei Li,1 Wenzhu Bi,1 Xiaolan Chen,1,* and Yufen Zhao1,2
1 College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, China
2 Department of Chemistry, Xiamen University, Xiamen, 361000, China
Email: [email protected]
Supplemental Materials
Synthesis of 1-azido-3-chloropropane
1-bromine-3-chloropropane 6.0 g (40 mmol) was dissolved in 40 mL DMSO, then NaN3 3.0 g
(43 mmol) was added slowly. The reaction mixture was stirred at room temperature for about 2
days, diluted with water (30 mL) and extracted by Et2O (3 × 60 mL). The combined organic
phase were dried over Na2SO4. The solvent was removed in vacuum and the crude product was
obtained as light yellow liquid 4.1 g (90%). The product were directly used in the next step
without further purification.
Synthesis of 7-(3-azidopropoxy)-5-hydroxy-flavone
Chrysin (5.1 g, 20 mmol) were dissolved in DMF (40) mL in a 100 mL 3-neck round bottom
flask equipped with a Teflon coated magnetic stir bar and reflux condenser, then 1-azido-3-
chloropropane (2.4 g, 20 mmol) were added at 60 °C in an oil bath. After being completely
dissolved, potassium carbonate (4.2 g, 35 mmol) and potassium iodide (0.3 g, 2 mmol) were
slowly added into the mixture. After completion of the reaction, as indicated by TLC (thin layer
chromatography), the mixture was extracted by CH2Cl2 (3 × 20 mL). The combined organic layer
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was dried over anhydrous Na2SO4. The solvent was removed in vacuum and the crude product
was purified by column chromatography on silica gel (petroleum ether : ethyl acetate = 10 : 1, v :
v). Compound 1 was obtained as amorphous solid 5.5 g.
General procedure for the synthesis of dialkyl alkynylphosphonates1
Terminal alkynes (6 mmol), dialkyl H-phosphonates (5 mmol), CuSO4·5H2O (20 mmol%) and
Et3N (35 mmol%) were dissolved in DMF (60 mL) in a 250 mL 3-neck round bottom flask at 55
°C. The reaction was tracked by 31P NMR. After completion of the reaction, the mixture was
extracted by CH2Cl2 (3 × 30 mL). The combined organic layer was washed with saturated
ammonium chloride aqueous solution and dried over anhydrous Na2SO4. The solvent was
removed in vacuum and the brown oily crude product was purified by column chromatography
on silica gel (petroleum ether : ethyl acetate = 1 : 1, v : v).
[1] Qu, Z. B; Chen, X. L; Yuan, J. W; Qu, L. B; Li, X; Wang, F. J; Ding, X. L; Zhao, Y. F. Can.
J. Chem. 2012, 90, 747-52.
1D and 2D NMR copies of product 6a and 6b
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Figure S 3. 13C NMR of compound 6aFigure S 4. DEPT-135 of compound 6a
Figure S 5. H-H COSY of compound 6a
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Figure S 11. H-H COSY of compound 6b
Figure S 12. HSQC of compound 6b1H NMR, 13C NMR,31P NMR copies of products 1-5 and 7
NN
NP O
OOO
O
OHO
NN
NP O
OOO
O
OHO
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Figure S 13. 1H NMR of compound 1a
Figure S 14. 13C NMR of compound 1a
NN
NP O
OOO
O
OHO
NN
N O
PO
OO
O
OH O
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Figure S 15. 31P NMR of the compound 1a
Figure S 16. 1H NMR of compound 1b
NN
N O
PO
OO
O
OH O
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Figure S 17. 13C NMR of compound 1b
Figure S 18. 31P NMR of the compound 1b
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Figure S 19. 1H NMR of compound 2a
Figure S 20. 13C NMR of compound 2a
Figure S 21. 31P NMR of compound 2a