(Z,E)-Sinomenine oxime (6a). 1H NMR: (CDCl3, 400 MHz) δ
8.95 (s, 1H), 6.62 (d, J = 8.4 Hz, 1H), 6.53 (d, J = 8 Hz, 1H),
5.99 (s, 1H), 5.14 (d, J = 16 Hz, 1H), 4.90 (s, 1H), 3.80 (s, 3H),
3.52, (s, 3H), 2.43 (s, 3H); 13C NMR (CDCl3, 100 MHz): δ
150.9, 150.8, 144.9, 144.8, 131.0, 123.7, 118.0, 108.5, 104.6,
57.1, 55.9, 54.7, 47.8, 44.3, 42.7, 37.3, 35.9, 33.3, 24.1; IR
(KBr): 3402, 2911, 2836, 1638, 1611, 1583, 1485, 1438, 1277,
1205, 1152, 1067, 809, 746 cm−1; MS (ESI): m/z (%) [M + H]+
= 345.6 (100), 346.8 (40), 348.3 (8), [2M + H]+ = 689.6 (35),
16-dehydropregenolone acetate and its analogues 2a–2e. The
yields and reaction durations are listed in Table 1 in the text.
General procedure for the reduction of ketones and aldehydes
(Table 2, 3a–3i)
To a mixture of ketone/aldehyde (2 g), Aliquat 336 (0.08 eq.),
PTFE sand (2 g) and water (10 mL) was added KBH4 (0.8 eq.)
in portions. The mixture was mechanically stirred (400 rpm,
Teflon blade, D = 4 cm) at 20 °C or 60 °C for 1–6.5 h. TLC
showed the completion of the reaction. After stopping the reac-
tion, the crystalline product was suspended in water while the
sand precipitated on the bottom. The suspension was filtrated to
give 4a–4i in quantitative yields leaving the sand to be recov-
ered. The yields and reaction durations are listed in Table 2 in
the text.
690.5 (17), 691.4 (9), [3M + H]+ = 1033.1 (3), [M + Na]+
=
367.5 (4), [2M + Na]+ = 711.5 (30), 712.6 (15), 713.7 (5), [3M
+ Na]+ = 1055.2 (25), 1056.3 (15), 1057.3 (5); HRMS (ESI):
m/z [M + H]+ calcd for C19H24N2O4 + H: 345.1814; found
345.1816.
(Z,E)-N-Phenyl sinomenine hydrazone (6b). 1H NMR:
(CDCl3, 400 MHz) δ 7.84 (s, 1H), 6.53–7.27 (m, 7H), 6.03
(s,1H), 4.61–4.83 (m, 2H), 3.75–3.82 (m, 3H), 3.51–3.57 (m,
3H), 2.41–2.45 (m, 3H); 13C NMR (CDCl3, 100 MHz): δ 153.2,
152.6, 145.5, 144.8, 144.5, 139.3, 131.1, 129.0, 128.9, 123.4,
119.7, 118.8, 118.5, 117.9, 114.3, 113.1, 112.2, 108.9, 102.3,
57.3, 56.0, 54.9, 54.3, 48.0, 47.7, 47.1, 44.8, 43.2, 42.7, 38.0,
37.8, 35.5, 34.0, 31.6, 29.0, 24.2, 22.5, 14.0; IR (KBr): 3492,
3346, 2933, 2839, 1601, 1503, 1485, 1438, 1278, 1204, 1160,
1055, 796, 750 cm−1; MS (ESI): m/z (%) [M + H]+ = 420.6
(100), 421.7 (70), 422.7 (33); HRMS (ESI): m/z [M + H]+ calcd
for C25H29N3O3 + H: 420.2287; found 420.2288.
General procedure for the condensation of sinomenine
(Table 3, 5a)
A mixture of sinomenine 5a (2 g), NH2OH·HCl/PhNHNH2·HCl
(1.0 eq.), Aliquat 336 (0.08 eq.), PTFE sand (2 g) and water
(10 mL) was mechanically stirred (400 rpm, Teflon blade, D =
4 cm) at 60 °C for 1 h or 3 h. TLC showed the completion of the
reaction. The reaction mixture was decanted from the sand and
neutralized with ammonium hydroxide, and filtrated to give 6a/
6b in quantitative yields. The yields and reaction durations are
listed in Table 3 in the text.
Acknowledgements
We are grateful to NSFC for the financial support.
General procedure for the hydrolysis of esters (Table 4,
entry 1–6)
Notes and references
A mixture of ester (2 g), Aliquat 336 (0.08 eq.), KOH (1.5 eq.),
PTFE sand (2 g) and water (10 mL) was mechanically stirred
(400 rpm, Teflon blade, D = 4 cm) at 60 °C for 1–7 h. TLC
showed the completion of the reaction. After stopping the reac-
tion, the crystalline product was suspended in water while the
sand precipitated on the bottom. The suspension was filtrated to
give the corresponding products in quantitative yields leaving
the sand to be recovered. The yields and reaction durations are
listed in Table 4 in the text.
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NMR, IR, MS, mp and HRMS data of new compounds
4-(4-Nitrobenzoxy)benzyl 4-nitrobenzoate (4h). 1H NMR:
(CDCl3, 400 MHz) δ 8.40 (q, J = 8.8 Hz, 4H), 8.30 (dd, J = 8.8
Hz, J = 22 Hz, 4H), 7.22–7.24 (m, 1H), 7.14–7.15 (m, 2H), 5.44
(s, 2H), 3.88 (s, 3H); 13C NMR (CDCl3, 100 MHz): δ 164.7,
163.0, 151.4, 151.1, 150.9, 139.9, 135.6, 134.9, 131.7, 131.1,
123.9, 123.8, 123.1, 121.3, 113.1, 67.5, 56.3; IR (KBr): 1738,
1730, 1607, 1520, 1263, 1099, 852, 717 cm−1
; mp:
198–201 °C; MS (ESI): m/z (%) [M + Na]+ = 475.4 (5); HRMS
(ESI): m/z [M + Na]+ calcd for C22H16N2O9 + Na: 475.0753;
found 475.0761.
672 | Green Chem., 2012, 14, 668–672
This journal is © The Royal Society of Chemistry 2012