Chlorosuccinimide → 4-Chlorosampangine

HRID 260764Notes

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 cm1 ; 1H NMR (CDCl3) δ7.68 (ddd, 1 H, J=7.6, 7.6, 1.4 Hz), 7.81 (ddd, 1 H, J= 7.6, 7.6, 1.4 Hz), 7.95 (d, 1 H, J=5.9 Hz), 8.41 (dd, 1 H, J=7.6, 1.4 Hz), 8.76 (dd, 1 H, 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-093c3ab8fc9e4e87bbcf512cbb740a24
Source dataset: uspto-grants-1996_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05530004

Reaction notes

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