EXPERIMENTAL
Celangulin-V (1) was provided by the Institute of Pesticides, Northwest A&F University. Podophyllotoxin (2) was
provided by Prof. Xuan Tian, Lanzhou University.
1
13
H NMR and C NMR spectra were recorded on a Bruker AM-500 spectrometer in CDCl with TMS as internal
3
standard. Melting points were recorded on an electrothermal digital apparatus made in Beijing and were uncorrected. HR-MS
were recorded under ESI condition using a APEX II 49e (ESI) instrument. Optical rotation was measured by a Perkin–Elmer
Model 241 instrument. Analytical thin-layer chromatography (TLC) was carried out on precoated plates (silica gel), and spots
were visualized with H SO –EtOH. Separation and purification were carried out by column chromatography on silica gel
2
4
(200–300 mesh) (Qingdao Haiyang Chemical Group Co., P. R. China). Yields were not optimized. Succinic acid celangulin-V
ester (1a) and succinic acid podophyllotoxin ester (2a) were prepared by the literature method [3, 11]. Solvents were dried by
standard methods and distilled. The title compounds were synthesized under a nitrogen atmosphere.
Insecticidal activity was investigated using a leaf disc choice method. The concentration of the tested compounds was
5% in acetone [12].
Synthesis of 3. A mixture of celangulin-V (1) (0.079 g, 0.12 mmol) and succinic acid celangulin-V ester (1a) (0.076 g,
0.1 mmol), dimethylaminopyridine (DMAP, 0.012 g, 0.1 mmol), and N,N-dicyclohexylcarbodiimide (DCC, 0.042 g, 0.02 mmol)
in dry dichloromethane (DCM, 20 mL) was stirred for 3 h at 20°C. The resulting suspension was filtered, and saturated NH Cl
4
(30 mL) was added into the DCM layer. After extracting with dichloromethane (25 mL × 3), the organic layer was dried and
concentrated to give the crude product, which was then purified by silica gel column. A yield of 63.6% (0.089 g) of a white
[ꢀ]2D0
+
powder was obtained, mp 233–235°C,
+2° (c 0.6, MeOH), C H O HRMS/([M+Na] ) Calcd. (Found) 1429.5829
72 94 28
(1429.5833).
1
H NMR (CDCl , 500 MHz, δ, ppm, J/Hz): 5.47 (2H, d, J = 3.5), 5.36 (2H, d, J = 3.5), 1.96, 2.09 (4H, m), 6.51 (2H,
3
s), 2.53 (2H, d, J = 3.5), 5.77 (2H, dd, J = 3.5, J = 9.5), 6.04 (2H, d, J = 9.5), 4.88, 4.66 (4H, dd, J = 13.5), 1.72 (6H, s), 1.60
(6H, s), 1.47 (6H, s), 2.92 (2H, m), 2.37 (2H, m), 1.38 (12H, m), 0.97 (12H, m), 7.86 (4H, d, J = 8.0), 7.41 (4H, dd, J = 7.5,
J = 8.0), 7.55 (2H, dd, J = 7.5, J = 8.0), 2.09 (6H, s), 1.54 (6H, s), 3.47 (4H, m).
13
C NMR (CDCl , 125 MHz, δ, ppm): 75.5 (CH), 67.7 (CH), 42.1 (CH ), 69.6 (C), 92.2 (C), 75.9 (CH), 52.3 (CH),
3
2
73.4 (CH), 75.2 (CH), 51.5 (C), 84.4 (C), 61.8 (CH ), 24.7 (CH ), 29.8 (CH ), 25.9 (CH ), 176.8 (C=O), 175.6 (C=O), 169.6
2
3
3
3
(C=O), 169.5 (C=O), 165.6 (C=O), 21.1 (CH ), 20.5 (CH ), 133.5 (CH), 128.7 (2 × CH), 129.3 (C), 129.4 (2 × CH), 34.2
3
3
(CH), 34.1 (CH), 19.1 (CH ), 19.0 (CH ), 18.6 (CH ), 18.5 (CH ), 170.5 (C=O), 29.3 (CH ).
3
3
3
3
2
Synthesis of 4 and 5. Compound 4 was prepared from podophyllotoxin (2) and compound 5 from podophyllotoxin
(2) and succinic acid celangulin-V ester (1a) in the same way.
20
Compound 4 was obtained as a white powder, yield 60.4%, mp 180–182°C,
–50° (c 0.4, MeOH), C H O
48 46 18
[ꢀ]D
+
HRMS/([M+Na] ) Calcd. (Found) 933.2582 (933.2571).
1
H NMR (CDCl , 500 MHz, δ, ppm, J/Hz): 4.12 (2H, m), 4.62 (2H, d, J = 4.0), 6.55 (2H, s), 5.97 (2H, d, J = 1.5), 5.99
3
(2H, d, J = 1.5), 6.81 (2H, s), 5.95 (2H, d, J = 9.0), 2.92 (2H, m), 4.39 (2H, m), 4.19 (2H, m), 6.40 (4H, s), 3.76 (12H, s), 3.81
(6H, s), 2.77 (4H, m).
13
C NMR (CDCl , 125 MHz, δ, ppm): 173.6 (C=O), 45.5 (CH), 43.7 (CH), 128.0 (C), 106.9 (CH), 148.2 (C), 101.7
3
(CH ), 147.6 (C), 109.8 (2 × CH), 132.3 (C), 74.2 (CH), 38.6 (CH), 71.2 (CH ), 134.8 (C), 108.2 (CH), 152.7 (2 × C), 137.3
2
2
(C), 56.2 (2 × CH ), 60.8 (CH ), 172.9 (C=O), 29.1 (CH ).
3
3
2
20
Compound 5 was obtained as a white powder, yield 54.6%, mp 176–178°C,
–62° (c 0.5, MeOH), C H O
60 70 23
[ꢀ]D
+
HRMS/([M+Na] ) Calcd. (Found) 1181.4206 (1181.4218).
1
H NMR (CDCl , 500 MHz, δ, ppm, J/Hz): 5.48 (1H, d, J = 3.0), 5.36 (1H, d, J = 3.0), 1.95, 2.09 (2H, m), 6.53 (1H,
3
s), 2.53 (1H, d, J = 3.0), 5.77 (1H, dd, J = 3.0, J = 9.5), 6.05 (1H, d, J = 9.5), 4.88, 4.67 (2H, dd, J = 13.0), 1.73 (3H, s), 1.59
(3H, s), 1.51 (3H, s), 2.38 (1H, m), 2.81 (1H, m), 0.95 (6H, m), 1.38 (6H, m), 2.08 (3H, s), 1.55 (3H, s), 7.86 (2H, d, J = 8.0),
7.41 (2H, dd, J = 8.0, J = 7.5), 7.56 (1H, dd, J = 8.0, J = 7.5), 3.48 (2H, m), 2.73 (2H, m), 4.17 (1H, m), 4.61 (1H, d, J = 4.0),
6.53 (1H, s), 5.99 (2H, m), 6.79 (1H, s), 5.93 (1H, d, J = 9.0), 2.70 (1H, m), 4.39 (1H, m), 4.19 (1H, m), 6.40 (2H, s), 3.77 (6H,
s), 3.82 (3H, s).
13
C NMR (CDCl , 125 MHz, δ, ppm): 75.5 (CH), 67.6 (CH), 42.1 (CH ), 69.6 (C), 92.1 (C), 75.9 (CH), 52.3 (CH),
3
2
73.4 (CH), 75.2 (CH), 51.4 (C), 84.4 (C), 61.8 (CH ), 24.7 (CH ), 29.8 (CH ), 25.6 (CH ), 176.8 (C=O), 175.6 (C=O), 169.6
2
3
3
3
(C=O), 169.5 (C=O), 165.6 (C=O), 21.2 (CH ), 20.5 (CH ), 133.5 (CH), 128.7 (2 × CH), 129.4 (2 × CH), 129.5 (C), 34.3
3
3
509