Phthalimide potassium salt → HCID 69882885, compound

HRID 2119612Notes

Reaction equation

HRID 2119612 reaction equation
[C:1]1(=[O:11])[NH:5][C:4](=[O:6])[C:3]2=[CH:7][CH:8]=[CH:9][CH:10]=[C:2]12.[K].[F:13][C:14]1[CH:15]=[CH:16][C:17]2[C:22]3[C:23]4[C:52](=[O:53])[NH:51][C:50](=[O:54])[C:24]=4[C:25]4[C:26]5[C:31]([N:32]([C@@H:34]6[O:42][C@H:41]([CH2:43]OS(C)(=O)=O)[C@@H:39]([OH:40])[C@H:37]([OH:38])[C@H:35]6[OH:36])[C:33]=4[C:21]=3[NH:20][C:18]=2[CH:19]=1)=[CH:30][C:29]([F:49])=[CH:28][CH:27]=5>CN(C)C=O>[F:13][C:14]1[CH:15]=[CH:16][C:17]2[C:22]3[C:23]4[C:52](=[O:53])[NH:51][C:50](=[O:54])[C:24]=4[C:25]4[C:26]5[C:31]([N:32]([C@@H:34]6[O:42][C@H:41]([CH2:43][N:5]7[C:1](=[O:11])[C:2]8=[CH:10][CH:9]=[CH:8][CH:7]=[C:3]8[C:4]7=[O:6])[C@@H:39]([OH:40])[C@H:37]([OH:38])[C@H:35]6[OH:36])[C:33]=4[C:21]=3[NH:20][C:18]=2[CH:19]=1)=[CH:30][C:29]([F:49])=[CH:28][CH:27]=5.[C@@H:34]1([N:32]2[C:33]3[C:21]4[NH:20][C:18]5[CH:19]=[C:14]([F:13])[CH:15]=[CH:16][C:17]=5[C:22]=4[C:23]4[C:52](=[O:53])[NH:51][C:50](=[O:54])[C:24]=4[C:25]=3[C:26]3[C:31]2=[CH:30][C:29]([F:49])=[CH:28][CH:27]=3)[O:42][C@@H:41]2[CH2:43][O:38][C@@H:37]([C@@H:39]2[OH:40])[C@H:35]1[OH:36]

Participants

5

Reactant 2

HCID 24194345Phthalimide potassium saltHCID 86585637HCID 86585637, compound

Product 2

HCID 69882885HCID 69882885, compoundYield 21%HCID 69883429HCID 69883429, compoundYield 13%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

2,10-Difluoro-12,13-dihydro-12-[β-D-glucopyranosyl]-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione (1.0 g, 1.91 mmol) was dissolved in dry pyridine under nitrogen at room temperature and treated with flame-dried, powdered 4A molecular sieves (0.60 g). The mixture was cooled to −20° C. for 15 min before methanesulfonyl chloride (0.26 mL, 3.34 mmol, 1.75 eq.) was added neat. The flask was sealed and stored at 0° C. for 6 h prior to concentration in vacuo. Purification of the residue by flash chromatography on silica gel (elution with tetrahydrofuran/dichloromethane/methanol, 68:30:2) gave an enriched fraction (280 mg, 24%) containing the title compound as well as a small amount of other closely-spaced by-products which was carried on directly. Potassium phthalimide (0.45 g, 2.43 mmol) was added in one portion to a stirred solution of 2,10-difluoro-12,13-dihydro-12-[6-O-(methylsulfonyl)-β-D-glucopyranosyl]-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione (200 mg, 0.33 mmol) in anhydrous dimethylformamide (10 mL) before the mixture was heated to 130°0 C. for 3 h, cooled to ambient temperature, and concentrated down in vacuo overnight. The residue was then taken up in ethyl acetate (some tetrahydrofuran was added) and washed with 0.1N hydrochloric acid and brine. Following drying and solvent concentration, the residue was purified by flash chromatography on silica gel (elution with 7% methanol in chloroform) to yield 2,10-difluoro-12,13-dihydro-12-[6-deoxy-6-(phthalimido)-β-D-glucopyranosyl]-5H-indolo[2,3-a]pyrrolo[3,4-c]carbazole-5,7(6H)-dione (46 mg, 21%) as a yellow solid as well as the title compound (22 mg, 13%, 2 steps) also as a yellow solid.

Workup

  1. temperaturewas heated to 130°0 C
  2. concentrationconcentrated down in vacuo overnight
  3. additionwas added) and
  4. washwashed with 0.1N hydrochloric acid and brine
  5. customFollowing drying
  6. concentrationsolvent concentration
  7. customthe residue was purified by flash chromatography on silica gel (elution with 7% methanol in chloroform)

Sources & evidence

ORD record
ord-04c55f19b4af40d1a2f76baa0e3995a1
Source dataset
uspto-grants-2004_02
Patent number
US06686385B2

Reaction notes

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