Chlorosuccinimide → 4-Chlorosampangine

HRID 483837Notes

Reaction equation

[Cl:1]N1C(=O)CCC1=O.[CH:9]1[CH:10]=[CH:11][C:12]2[C:25](=[O:26])[C:24]3[C:16]4[C:17]([CH:21]=[CH:22][N:23]=3)=[CH:18][CH:19]=[N:20][C:15]=4[C:13]=2[CH:14]=1>CN(C=O)C>[CH:9]1[CH:14]=[C:13]2[C:15]3[C:16]4[C:24]([C:25](=[O:26])[C:12]2=[CH:11][CH:10]=1)=[N:23][CH:22]=[C:21]([Cl:1])[C:17]=4[CH:18]=[CH:19][N:20]=3

Participants

Conditions

Temperature: 100 °C

Procedure

N-Chlorosuccinimide (200 mg, 1.5 mmol) was added to a suspension of sampan-gine (232 mg, 1.0 mmol) in DMF (10 mL) and the mixture stirred at 100° C. for 24 h. The reaction was then poured onto H2O (100 mL) and the solids isolated by filtration. The crude product was purified by column chromatography eluting with CHCl3 /EtOAc (9:1) to give 4-chlorosampangine (21) (142 mg, 53%). Crystallization from EtOAc provided an analytical sample: mp 262°-263° C.; IR (KBr) 1670, 1590, 1410, 1315, 1278, 1240, 1230, 1000, 790, 758, 725, 610 cm-1 ; 1H NMR (CDCl3) δ 7.68 (ddd, 1H, J=7.6, 7.6, 1.4 Hz), 7.81 (ddd, 1H, J=7.6, 7.6, 1.4 Hz), 7.95 (d, 1H, J=5.9 Hz), 8.41 (dd, 1H, J=7.6, 1.4 Hz), 8.76 (dd, 1H, J=7.6, 1.4 Hz), 8.93 (d, 1H, J=5.9 Hz), 9.09 (s, 1H); 13C NMR (CDCl3) 115.7 (1), 120.0 (0), 125.6 (1), 128.5 (1), 131.7 (1), 132.0 (0), 132.2 (0), 134.8 (1), 135.0 (0), 136.9 (0), 146.0 (0), 147.2 (1), 148.2 (1), 151.5 (0), 181.2 (0) ppm; Anal. calcd for C15H7ClN2O: C 67.56, H 2.65, N 10.50; found C 67.63, H 2.52, N 10.54.

Workup

additionThe reaction was then poured onto H2O (100 mL)
customthe solids isolated by filtration
customThe crude product was purified by column chromatography
washeluting with CHCl3 /EtOAc (9:1)

Sources & evidence

ORD record: ord-f32a4b275fb44f8480257c09ff17f4d0
Source dataset: uspto-grants-1993_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05227383

Reaction notes

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