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in vacuo. Purication using ash column chromatography affor- 3589, 2943, 1578, 1544, 1263, 1187, 979, 874, 763, 665 cmꢁ1; 1H
ded the products, namely, 12, 19, 23, and 26a–d.
NMR (300 MHz, CDCl3): d 7.37 (d, J ¼ 8.1 Hz, 2H), 6.93 (d, J ¼ 7.8
Hz, 2H), 5.96 (s, 1H), 4.70 (s, 1H), 4.61 (m, 2H), 4.42–4.39 (m,
2H), 3.97 (d, J ¼ 9.9 Hz, 1H), 2.18 (bs, 1H), 1.55 (s, 3H), 1.31 (s,
3H), 1.23 (m, 1H), 0.61–0.59 (m, 1H), 0.54 (m, 1H), 0.45 (m, 1H),
Physical data of the developed compounds
Bis(1H-benzo[d][1,2,3]triazol-1-yl)methanethione (2). Yellow 0.34 (m, 1H) ppm; 13C NMR (75 MHz, CDCl3): d 155.9, 137.4,
crystals; IR (KBr) nmax 1597, 1536, 1067, 1007, 959, 891, 728, 692, 127.4 (2C), 114.9 (2C), 112.0, 105.1, 82.0, 80.2, 77.7, 77.6, 62.0,
650 cmꢁ1; 1H NMR (300 MHz, CDCl3): d 8.27 (d, J ¼ 8.4 Hz, 2H), 26.6, 26.1, 19.0, 3.4, 2.6 ppm.
8.22 (d, J ¼ 8.1 Hz, 2H), 7.74 (t, J ¼ 7.8 Hz, 2H), 7.60 (t, J ¼ 7.5 Hz,
30-O-(4-((Cyclopropyl)(1H-benzotriazolylmethanethionyl)
2H) ppm; 13C NMR (75 MHz, CDCl3): d 169.6 (2C), 146.7 (2C), methyl)phenyl)-10,20-O-isopropylidine-a-D-xylofuranose-50-1H-
133.0 (2C), 130.5 (2C), 126.9 (2C), 120.9 (2C), 113.8 (2C) ppm.
benzotriazolecarbothioate (17). The compound 16 (0.672 g, 2.0
30-O-(4-(Hydroxy)(cyclopropyl)methyl)-phenyl-10,20:50,60-di-O- mmol) aer treatment with 2 (1.193 g, 4.2 mmol) and Et3N (0.4
isopropylidene-a-D-glucofuranose (10). Colorless solid; IR (KBr) equiv.) in anhydrous CH2Cl2 (20 mL) was stirred for 12 h at
nmax 3641, 2983, 2942, 1616, 1589, 1105, 1087, 889, 764 cmꢁ1; 1H room temperature. The crude product was puried by ash
NMR (300 MHz, CDCl3): d 7.37 (d, J ¼ 8.4 Hz, 2H), 6.97 (d, J ¼ 8.4 column chromatography (10% ethyl acetate/n-hexane) to afford
Hz, 2H), 5.92 (d, J ¼ 3.3 Hz, 1H), 4.72 (s, 1H), 4.60 (d, J ¼ 3.6 Hz, a light yellowish viscous liquid 17 (0.825 g, 63%, Rf ¼ 0.70, 30%
1H), 4.48–4.46 (m, 1H), 4.33 (d, J ¼ 7.8 Hz, 1H), 4.15–4.11 (m, ethyl acetate/n-hexane). MS: m/z 659 [M + H]+; IR (Nujol) nmax
2H), 3.96 (d, J ¼ 8.4 Hz, one isomer), 3.45 (d, J ¼ 7.8 Hz, other 1726, 1613, 1545, 1107, 1055, 1044, 876, 784, 637 cmꢁ1; 1H NMR
isomer), 3.23 (s, 1H), 1.55, 1.43, 1.32 and 1.30 (each s, each 3H), (300 MHz, CDCl3): d 8.33 (d, J ¼ 7.8 Hz, 1H), 8.31–8.07 (m, 3H),
0.66–0.60 (m, 1H), 0.58–0.53 (m, 1H), 0.47–0.43 (m, 1H), 0.38– 7.63–7.55 (m, 2H), 7.46–7.44 (m, 4H), 6.99 (d, J ¼ 8.4 Hz, 2H),
0.30 (m, 1H), 0.24–0.19 (m, 1H) ppm.
6.06 (d, J ¼ 3.3 Hz, 1H), 5.16–5.14 (m, 2H), 4.96–4.91 (m, 2H),
O-(Cyclopropyl(4-(10,20:50,60-di-O-isopropylidine-a-D-gluco- 4.71 (m, 1H), 4.25 (d, J ¼ 9.3 Hz, 1H), 1.57 (s, 3H), 1.45–1.42 (m,
furanoxy)phenyl)methyl)-1H-benzo[d][1,2,3]triazole-1-carbothioate 1H), 1.33 (s, 3H), 0.79–0.70 (m, 2H), 0.58 (m, 1H), 0.47 (m, 1H)
(11). The compound 10 (0.406 g, 1.0 mmol) aer treatment with ppm; 13C NMR (75 MHz, CDCl3): d 182.4, 167.5, 155.8, 146.2,
2 (0.31 g, 1.1 mmol) and Et3N (0.3 equiv.) in dry CH2Cl2 (15 mL) 146.1, 134.8, 131.1, 130.7, 130.4, 129.2 (2C), 126.1, 125.9, 125.7,
was stirred for 8 h at room temperature. The crude product was 120.5, 120.2, 115.2 (2C), 114.8, 113.5, 112.4, 105.2, 82.1, 80.1,
puried by ash column chromatography (10% ethyl acetate/n- 76.7, 69.8, 53.9, 26.7, 26.2, 16.7, 6.5, 6.1 ppm.
hexane) to afford a yellowish viscous liquid, 11, (0.436 g, 77%, Rf
30-O-(4-(Cyclopropyl(hydroxy)methyl)phenoxy)-10,20-O-iso-
¼ 0.60, 20% ethyl acetate/n-hexane). IR (Nujol) nmax 1744, 1616, propylidine-a-D-glucofuranoxy-50-1H-benzo[d][1,2,3]triazole-1-
1579, 1088, 1067, 1054, 986, 974, 734 cmꢁ1; 1H NMR (300 MHz, carbothioate (18). Viscous liquid; Rf ¼ 0.50, 60% ethyl acetate/n-
CDCl3): d 8.15 (d, J ¼ 8.1 Hz, 1H), 8.10 (d, J ¼ 8.4 Hz, 1H), 7.62 (t, hexane); MS: m/z 498 [M + H]+; IR (Nujol) nmax 3568, 2921, 1663,
J ¼ 7.5 Hz, 1H), 7.50 (m, 1H), 7.46 (d, J ¼ 8.7 Hz, 2H), 6.97 (d, 1557, 1211, 1189, 794, 768, 654 cmꢁ1
;
1H NMR (300 MHz,
J ¼ 8.4 Hz, 2H), 5.90 (s, J ¼ 3.6 Hz, 1H), 4.71 (d, J ¼ 2.7 Hz, 1H), CDCl3): d 8.35 (d, J ¼ 8.1 Hz, 1H), 8.09 (d, J ¼ 8.1 Hz, 1H), 7.60
4.59 (d, J ¼ 3.6 Hz, 1H), 4.43 (dd, J ¼ 6.0, 7.2 Hz, 1H), 4.31–4.25 (dd, J ¼ 7.5, 7.2 Hz, 1H), 7.46 (dd, J ¼ 7.8, 7.2 Hz, 1H), 7.34 (d,
(m, 2H), 4.13–4.08 (m, 2H), 1.54 (s, 3H), 1.42 (s, 3H), 1.29 (s, 6H), J ¼ 8.4 Hz, 2H), 6.97 (d, J ¼ 7.8 Hz, 2H), 6.06 (s, 1H), 5.17–5.16
0.78–0.70 (m, 2H), 0.68–0.56 (m, 1H), 0.50–0.43 (m, 1H) ppm; (m, 2H), 4.94 (d, J ¼ 11.4 Hz, 1H), 4.92 (m, 1H), 4.71 (d, J ¼ 3.0
13C NMR (75 MHz, CDCl3): d 167.6, 156.1, 146.1, 134.4, 130.7, Hz, 1H), 3.94 (d, J ¼ 8.1 Hz, 1H), 2.18 (bs, 1H), 1.57 (s, 3H), 1.34
130.4, 129.1 (2C), 126.1, 120.2, 115.3 (2C), 113.6, 112.0, 109.1, (s, 3H), 1.14 (m, 1H), 0.59 (m, 1H), 0.51 (m, 1H), 0.43 (m, 1H),
105.2, 82.0, 80.3, 79.7, 72.1, 66.9, 54.0, 26.7, 26.6, 26.1, 25.1, 0.31 (m, 1H) ppm; 13C NMR (75 MHz, CDCl3): d 182.4, 155.7,
16.9, 6.5, 6.2 ppm; MS: m/z 568 [M + H]+; anal. calcd for 146.2, 137.6, 131.1, 130.4, 127.4 (2C), 125.9, 120.4, 115.0 (2C),
C
29H33N3O7S: C, 61.36; H, 5.86; N, 7.40; found: C, 61.51; H, 5.98; 114.8, 112.3, 105.2, 82.2, 80.1, 77.7, 77.6, 69.9, 26.7, 26.2, 19.0,
N, 7.57.
30-O-(4-(Cyclopropylmethyl)phenyl)-10,20,50,60-di-O-isopro-
3.4, 2.6 ppm.
50-O-(Benzothiazol-2-yl)-30-O-(4-(cyclopropylmethyl)phenyl)-
pylideneglucofuranose (12). Colorless viscous liquid; yield 85%; 10,20-O-isopropylidine-a-D-xylofuranose (19). Viscous liquid;
Rf ¼ 0.68 (20% ethyl acetate/n-hexane); MS: m/z 391 [M + H]+; IR yield 51%; Rf ¼ 0.75 (20% ethyl acetate/n-hexane); 6 equivalents
(Nujol) nmax 2938, 1597, 1072, 1032, 981, 972, 875, 766, 732 of (TMS)3SiH has been used. IR (Nujol) nmax 3013, 1598, 1535,
1
cmꢁ1; 1H NMR (300 MHz, CDCl3): d 7.26 (d, J ¼ 8.4 Hz, 2H), 6.96 1075, 1021, 845, 756, 644 cmꢁ1; H NMR (300 MHz, CDCl3): d
(d, J ¼ 8.4 Hz, 2H), 5.93 (d, J ¼ 3.3 Hz, 1H), 4.73 (d, J ¼ 3.0 Hz, 7.64–7.60 (m, 2H), 7.34–7.32 (m, 3H), 7.20 (dd, J ¼ 7.8, 7.5 Hz,
1H), 4.62 (d, J ¼ 3.9 Hz, 1H), 4.48 (dd, J ¼ 12.3, 5.7 Hz, 1H), 4.33 1H), 6.94 (d, J ¼ 7.8 Hz, 2H), 6.01 (s, 1H), 4.97–4.81 (m, 4H), 4.65
(dd, J ¼ 13.5, 3.0 Hz, 1H), 4.15–4.12 (m, 2H), 3.48 (d, J ¼ 7.8 Hz, (m, 1H), 3.37–3.34 (m, 1H), 2.04 (d, J ¼ 3.3 Hz, 1H), 1.56 (s, 3H),
2H), 2.72–2.55 (m, 1H), 1.55 (s, 3H), 1.44 (s, 3H), 1.32 (s, 3H), 1.42–1.40 (m, 1H), 1.32 (s, 3H), 0.73–0.71 (m, 1H), 0.57 (m, 1H),
1.31 (s, 3H), 1.17–1.09 (m, 1H), 0.68–0.60 (m, 1H), 0.48–0.43 (m, 0.37–0.29 (m, 2H) ppm; 13C NMR (75 MHz, CDCl3): d 172.3,
2H), 0.26–0.18 (m, 1H) ppm; 13C NMR (75 MHz, CDCl3): d 156.1, 155.6, 149.0, 137.4, 132.0, 128.4 (2C), 125.9, 123.5, 121.2, 120.8,
134.9, 128.0 (2C), 115.1 (2C), 111.9, 109.0, 105.1, 82.0, 80.3, 79.6, 115.1 (2C), 112.2, 105.3, 82.0, 80.2, 77.5, 68.8, 48.7, 26.7, 26.2,
72.1, 66.9, 47.2, 26.7, 26.6, 26.1, 25.1, 17.4, 4.2, 1.7 ppm.
20.2, 6.3, 6.0 ppm; MS: m/z 454 [M + H]+; anal. calcd for
25H27NO5S: C, 66.20; H, 6.00; N, 3.09; found: C, 66.37; H, 6.03;
30-(4-((Cyclopropyl)hydroxymethyl)phenyl)-10,20-O-isopro-
C
pylidene-a-D-xylofuranose (16). Viscous liquid; IR (Nujol) nmax N, 3.13.
31590 | RSC Adv., 2015, 5, 31584–31593
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