RSC Advances
Page 6 of 7
DOI: 10.1039/C4RA16342G
2.36 (m, 2H), 2.02–0.85 (m, 38H), 0.67 (s, 3H); FTIR (KBr,
cm−1): 2939, 2907, 2821, 1753, 1620, 1195.
A mixture of 6,7ꢀDihydroxycoumarin (0.1g, 0.56 mmol) and
Cs2CO3 (0.36g, 1.12 mmol) was refluxed in dry CH3CN for 2 h
and then compound 6 (0.49 g, 0.84 mmol) was added to it. The
reaction mixture was then allowed to reflux for 36 h. Then the
organic solvent was evaporated under reduced pressure and water
was added to the crude mass. Then reaction mixture was
extracted with 2% CH3OH in CHCl3. Evaporation of the solvent
gave the crude product which was purified by column
chromatography using CHCl3 to 1% CH3OH in CHCl3 as eluents
to afford the pure compound 1 in 71 % yield (0.0.27 g), mp 192
0C.1H NMR (400 MHz, CDCl3): δ 7.87 (s, 1H), 7.60 (d, 1H, J = 8
Hz), 6.99 (s, 1H), 6.98 (s, 1H), 6.30 (d, 1H, J = 8 Hz), 6.20 (brs,
1H), 5.37ꢀ 5.30 (m, 3H), 5.17 (s, 2H), 4.70 (brs, 1H), 2.36 (d, 2H,
J = 8 Hz), 2.03–0.85 (m, 38H), 0.67 (s, 3H); 13C NMR (100
MHz, CDCl3): δ 165.7, 161.4, 149.2, 148.7, 144.9, 143.3, 142.4,
138.8, 124.9, 123.3, 113.8, 112.7, 112.1, 100.8, 62.8, 62.6, 56.6,
56.1, 51.0, 49.9, 42.2, 39.6, 39.5, 37.8, 36.8, 36.5, 36.1, 35.8,
31.8, 31.7, 28.2, 28.0, 27.6, 24.2, 23.8, 22.8, 22.5, 21.0, 19.2,
18.7, 11.8; FTIR (KBr, cm−1): 3391, 2935, 2867, 1725, 1627;
HRMS (TOF MS ES+): required 685.4091 (M+), 708.3989 (M +
Na+), found 685.3961 (M+), 708.3571 (M + Na+).
Azido-acetic acid 17-(1,5-dimethyl-hexyl)-10,13-dimethyl-
2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-
cyclopenta[a]phenanthren-3-yl ester (3):
To a stirred solution of compound 2 (0.5 g, 1.08 mmol) in
CH3CN (20 mL) NaN3 was added (0.11 g, 1.6 mmol) and the
reaction mixture was refluxed for 5 h. The progress of reaction
was monitored by TLC. After the total consumption of the halide,
solvent was evaporated off and water was added. The reaction
mixture was extracted with CHCl3. Evaporation of the solvent
gave the crude azide product 3 (0.45 g, yield 89%, mp 116 °C),
which after recrystallization from diethyl ether was directly used
in the next step. FTIR (KBr, cm−1): 2938, 2107, 1747, 1213.
(4-Hydroxymethyl-[1,2,3]triazol-1-yl)-acetic acid 17-(1,5-
dimethyl-hexyl)-10,13-dimethyl
2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-
cyclopenta[a]phenanthren-3-yl ester (4):
Acknowledgments
Compound 3 (0.6 g, 1.28 mmol) was dissolved in ethanol (40
mL) and propergyl alcohol (0.12 ml, 1.92 mmol) was added to
this solution followed by addition of 4 ml of saturated CuSO4
solution and Cu turning (0.75 mg). Then the reaction mixture was
refluxed for 6 h at 90 oC. After completion, reaction mixture was
filtered through celite bed. The filtrate was evaporated off and the
crude mass was extracted with 2% CH3OH in CHCl3 and dried
over anhydrous Na2SO4. Evaporation of the solvent gave the
crude product which was purified by column chromatography
using 70% ethyl acetate in petroleum ether to afford compound 4
We thank DST, New Delhi, India for providing facilities in the
university under DSTꢀPURSE program. SP thanks CSIR, New
Delhi, India for a fellowship.
References
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1
(0.53 g, yield 78%), mp 178 °C. H NMR (400 MHz, CDCl3): δ
7.68 (s, 1H), 5.37 (d, 1H, J = 4 Hz), 5.14 (s, 2H), 4.81 (s, 2H),
4.70 (m, 1H), 2.36 (d, 2H, J = 8 Hz), 1.99–0.85 (m, 38H), 0.67 (s,
3H) (signal for –OH is not found due to broadening); 13C NMR
(100 MHz, CDCl3): δ 165.7, 148.2, 138.9, 123.3, 123.2, 76.5,
56.6, 56.4, 56.1, 51.0, 49.9, 42.3, 39.6, 39.5, 37.8, 36.8, 36.5,
36.1, 35.8, 31.88, 31.80, 28.2, 28.0, 27.6, 24.2, 23.8, 22.8, 22.5,
21.0, 19.2, 18.7, 11.8; FTIR (KBr, cm−1): 3487, 3401, 2960,
2939, 1749, 1727, 1468, 1230, 1212.
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Compound 1:
To a stirred solution of 4 (0.5 g, 0.95 mmol) in 20 mL dry CH2Cl2
was added methanesulfonyl chloride (0.11 mL, 1.42 mmol) and
NEt3 (0.26 mL, 1.9 mmol) at 0 oC. The mixture was then allowed
to stir for 30 min at room temperature. The progress of the
reaction was monitored by TLC. After completion of reaction,
solvent was evaporated off and the crude mass was extracted with
CHCl3 to afford compound 5. Without characterization
compound 5 was dissolved in dry THF (15 mL). To this solution
LiBr (0.16 g, 1.9 mmol) was added and the mixture was stirred
for 8 h at room temperature. After completion of the reaction,
THF was evaporated off and the organic compound was extracted
with CHCl3 (3 x 20 mL), dried over Na2SO4. Removal of CHCl3
gave solid product 6 (0.48 g, yield 86 %) which was directly used
in the next step without characterization.
4. (a). X. Sui, X. Feng, M. A. Hempenius and G. Julius Vancso, J. Mater.
Chem. B, 2013, 1, 1658; (b) H. Svobodova, V. N.oponen, E. Kolehmainen
and E. Sievanen, RSC Adv., 2012, 2, 4985; (c) Y. Gao, J. Lu, J. Wu, J. Hu
and Y. Ju, RSC Adv., 2014,4, 63539; (d) B. Zoetebier, M. A. Hempenius
and G. J. Vancso, Chem. Commun., 2015, DOI: 10.1039/C4CC06988A,
(e) T. He, K. Li, N. Wang, Y. X..Liao, X. Wang and X. Q. Yu, Soft
Matter, 2014, 10, 3755.
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