20
1
(0.5 g, 26%), mp 136–138ꢃÑ, [ꢁ] –37ꢃ (c 1, MeOH). Í NMR spectrum (400 MHz, ÑDCl , ꢉ, ppm, J/Hz): 0.74–2.25 (20Í,
D
3
m, ent-caurane framework), 0.81 (3Í, s, Í -20), 1.17 (3Í, s, Í -18), 1.94–2.06 (30Í, m, 10AcO), 3.61–5.33 (19H, m, sophorosyl
3
3
and glucuronate residues), 3.73 (3Í, s, Í -7 ), 4.78 (1H, s, H -17), 5.05 (1Í, s, Í -17), 5.88 (1Í, d, J = 7.9, Í-1 ).
3
A
B
13
C NMR spectrum (100 MHz, ÑDCl , ꢉ, ppm): 16.34 (CH , Ñ-20), 19.21 (CH , Ñ-2), 20.57 (CH , Ñ-11), 20.66–20.95
3
3
2
2
[CH , 10 ÑÍ Ñ(Î)], 21.87 (CH , Ñ-6), 28.83 (CH , Ñ-18), 37.47 (CH , Ñ-3), 38.05 (CH , Ñ-12), 39.56 (C, Ñ-10), 40.76
3
3
2
3
2
2
(CH , Ñ-1), 41.46 (CH , Ñ-7), 42.76 (C, Ñ-8), 43.09 (C, Ñ-4), 44.47 (CH , Ñ-14), 47.47 (CH , Ñ-15), 52.99 (CH , Ñ-7 ),
2
2
2
2
3
53.64 (CH, Ñ-9), 56.99 (CH, Ñ-5), 62.14 (CH , Ñ-6 ), 62.56 (CH , Ñ-6 ), 68.46–77.56 (CH, C-2 , 3 , 4 , 5 , 2 , 3 , 4 , 5 , 2 ,
2
2
3 , 4 , 5 ), 86.45 (C, C-13), 90.98 (CH, C-1 ), 96.52 (CH, C-1 ), 100.71 (CH, C-1 ), 104.73 (CH , C-17), 152.88 (C, C-16),
2
+
166.89 (C, C-6 ), 169.45–170.77 (C, CH C(O)), 175.47 (C, C-19). Mass spectrum (ESI), m/z 1275.6 [M + Na] (calcd for
3
Ñ Í NaÎ , 1275.5).
59 80
29
(ꢂ-D-Glucopyranosyluronhydrazide)-13-O-[(3ꢅ,4ꢅ,6ꢅ-tri-O-acetyl-ꢂ-D-glucopyranosyl)-(1ꢅꢆ2ꢁ )-(3 ,4 ,6 -tri-O-
acetyl-ꢂ-D-glucopyranosyl)]-ent-caur-16-en-19-oate (8). A solution of 7 (0.1 g, 0.079 mmol) in MeOH (1 mL) was treated
dropwise with hydrazine monohydrate (0.076 mL, 1.572 mmol) and stirred for 12 h at 20°C. The resulting precipitate of
hydrazine acetate was filtered off. The solvent was distilled at reduced pressure to afford 8 (0.04 g, 61% yield) as a yellow oil,
20
–1
[ꢁ] –30ꢃ (c 0.1, MeOH). IR spectrum (film, ꢊ, cm ): 3200–3400 (NH), 1726 [Ñ(Î)ÎÑ], 1654 (C=C and amide I), 1544 (and
D
1
amide II). Í NMR spectrum (600 MHz, ÑD OD, ꢉ, ppm, J/Hz): 0.76–2.19 (20Í, m, ent-caurane framework), 0.96 (3Í, s,
3
Í -20), 1.19 (3Í, s, Í -18), 3.10–5.08 (23H, m, sophorosyl and glucuronate residues, H -17, Í -17, NH ), 5.41 (1Í, d,
3
3
A
B
2
13
J = 7.5, Í-1 ), 9.19 (1Í, br.s, NH). C NMR spectrum (100 MHz, ÑD OD, ꢉ, ppm): 13.65 (CH , Ñ-20), 16.18 (CH , Ñ-2),
3
3
2
19.07 (CH , Ñ-11), 23.13 (CH , Ñ-6), 28.71 (CH , Ñ-18), 38.97 (CH , Ñ-3), 39.25 (CH , Ñ-12), 40.65 (CH , Ñ-10), 41.80
2
2
3
2
2
2
(CH , Ñ-1), 43.51 (CH , Ñ-7), 44.28 (C, Ñ-8), 44.85 (C, Ñ-4), 45.02 (CH , Ñ-14), 47.71 (CH , Ñ-15), 56.59 (CH, Ñ-9), 58.44
2
2
2
2
(CH, Ñ-5), 62.69–62.90 (CH , Ñ-6 , C-6 ), 71.45–78.36 (CH, C-2 , 3 , 4 , 5 , 2 , 3 , 4 , 5 , 2 , 3 , 4 , 5 ), 82.42 (C,
2
C-13), 87.48 (CH, C-1 ), 95.45 (CH, C-1 ), 97.14 (CH, C-1 ), 105.17 (CH , C-17), 169.75 (C, C-16), 172.15 [C, C-6 ],
2
+
178.21 (C, C-19). Mass spectrum (MALDI), m/z 857.6 [M + Na] (calcd for C H N NaO , 857.4).
38 60
2
18
(Methyl-4 ꢅ-deoxy-ꢁ-L-threo-hex-4-enepyranosyluronate)-13-O-[(3ꢅ,4ꢅ,6ꢅ-tri-O-acetyl-ꢂ-D-glucopyranosyl)-
(1ꢅꢆ2ꢁ )-(3 ,4 ,6 -tri-O-acetyl-ꢂ-D-gluycopyranosyl)]-ent-caur-16-en-19-oate (9). A solution of 7 (0.05 g, 0.04 mmol) in
anhydrous MeOH (10 mL) was treated dropwise with freshly prepared NaOMe (0.02 g, 0.4 mmol), stirred for 3 h at 20°C, and
neutralized with HCl solution (0.1%, 3 mL). The resulting precipitate was filtered off. The solvent was evaporated at reduced
pressure. The residue was chromatographed over silica gel (CH Cl –MeOH, 7:1) to produce 9 (0.01 g, 27% yield) as a yellow
2
2
20
1
oil, [ꢁ] –35ꢃ(c 0.3, MeOH). Í NMR spectrum (600 MHz, ÑD OD, ꢉ, ppm,J/Hz): 0.80–2.30 (20Í, m, ent-caurane framework),
D
3
0.95 (3Í, s, Í -20), 1.19 (3Í, s, Í -18), 3.14–3.89 (12H, m, sophorosyl residue), 3.79 (3Í, s, Í -7 ), 4.21 (1Í, t, J = 4.3,
3
3
3
Í-2 ), 4.61 (1Í, br.dd, J = 7.7, 5.6, Í-3 ), 4.85 (1Í, s, H -17), 5.20 (1Í, s, Í -17), 6.14 (1H, d, J = 4.1, Í-4 ), 6.17 (1Í,
A
B
+
+
+
+
d, J = 7.7, Í-1 ). Mass spectrum (ESI), m/z: 837.5 [M + Na] , 853.5 [M + Ê] (calcd for [M + Na] 837.4, [M + Ê] 853.3).
C H O .
39 58 18
The antibacterial and antifungal activities were studied using serial dilutions in liquid growth media and published
methods [18, 19].
ACKNOWLEDGMENT
The work was supported financially by the Russian Science Foundation (Grant No. 14-50-00014).
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Food Chem. Toxicol., 46, S54 (2008).
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M. Wang, H. Qi, J. Li, Y. Xu, and H. Zhang, Food Chem. Toxicol., 86, 217 (2015).
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