Sodium Iodide → HCID 69593265, compound

HRID 480582Notes

Reaction equation

HRID 480582 reaction equation
[F:1][C:2]1[C:3]([F:53])=[CH:4][C:5]2[C:10]3[C:11]4[C:50](=[O:51])[NH:49][C:48](=[O:52])[C:12]=4[C:13]4[C:14]5[C:19]([N:20]([C@@H:22]6[O:43][C@H:42]([CH2:44][OH:45])[CH2:41][C@H:32]([O:33][CH2:34][C:35]7[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=7)[C@H:23]6[O:24][CH2:25][C:26]6[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=6)[C:21]=4[C:9]=3[NH:8][C:6]=2[CH:7]=1)=[CH:18][C:17]([F:46])=[C:16]([F:47])[CH:15]=5.C(N(CC)CC)C.CS(Cl)(=O)=O.[Na+].[I-:67]>ClCCl.CN(C1C=CN=CC=1)C.CC(C)=O>[F:1][C:2]1[C:3]([F:53])=[CH:4][C:5]2[C:10]3[C:11]4[C:50](=[O:51])[NH:49][C:48](=[O:52])[C:12]=4[C:13]4[C:14]5[C:19]([N:20]([C@@H:22]6[O:43][C@H:42]([CH:44]([I:67])[OH:45])[CH2:41][C@H:32]([O:33][CH2:34][C:35]7[CH:36]=[CH:37][CH:38]=[CH:39][CH:40]=7)[C@H:23]6[O:24][CH2:25][C:26]6[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=6)[C:21]=4[C:9]=3[NH:8][C:6]=2[CH:7]=1)=[CH:18][C:17]([F:46])=[C:16]([F:47])[CH:15]=5

Participants

8

Reactant 4

HCID 5238Sodium IodideHCID 8471TriethylamineHCID 31297Methanesulfonyl chlorideHCID 20758621HCID 20758621, compound

Product 1

HCID 69593265HCID 69593265, compoundYield 39%

Reagents, catalysts & solvents 3

HCID 142844-(Dimethylamino)pyridineCatalystHCID 180AcetoneSolventHCID 6344DichloromethaneSolvent

Procedure

A mixture of 2, 3, 9, 10-tetrafluoro-12-(2, 3-di-O-benzyl-4-deoxy-β-D-glucopyranosyl)-6, 7, 12, 13-tetrahydro(5H)indolo[2, 3-a]pyrrolo[3, 4-c]carbazole-5, 7-dione (2.00 g, 2.76 mmol) and freshly activated and pulverized 4A molecular sieves (0.60 g) in 100 mL of dichloromethane was cooled at 5C. under Ar and triethylamine (0.77 mL, 5.52 mmol), DMAP (0.20 g, 1.64 mmol) and methanesulfonyl chloride (0.32 mL, 4.14 mmol) were added sequentially. The mixture was stirred at the same temperature for 2 h and then it was filtered and the filter-cake was washed with ethyl acetate. The flitrate was diluted with ethyl acetate (200 mL) and ether (50 mL) and then it was washed (H2O×2, brine), dried (MgSO4) and evaporated to give a yellow glass. This material was taken up in 100 mL of acetone, NaI ( ) was added and the mixture was heated to reflux under Ar for 18 h. The cooled mixture was then evaporated to dryness and the residue was taken up in 10 mL of ethyl acetate, washed (H2O×2, brine) dried (MgSO4) and evaporated. The resulting solid was chromatographed (SiO2/2-32% ethyl acetate-hexane) to give the title compound (0.90 g, 39%) as an amorphous yellow solid: 1H NMR (CDCl3, 400 MHz) δ10.17 (s, 1H), 9.10 (dd, J=10.6, 8.4 Hz, 1H), 9.02 (dd, J=10.6, 8.5 Hz, 1H), 7.55 (m, 2H), 7.35 (m, 6H), 6.92 (t, J=7.4 Hz, 1H), 6.76 (t, J=7.6 Hz, 2H), 6.20 (d, J=7.6 Hz, 2H), 5.75 (d, J=9.2 Hz, 1H), 4.77 and 4.71 (ab q, J=11.5 Hz, 2H), 4.13 (m, 2H), 3.99 (t, J=8.7 Hz, 1H), 3.80 (m, 2H 3.63 (d, J=9.0 Hz, 1H), 3.48 (d, J=10.8 Hz, 1H), 2.42 (m, 1H), 2.32 (m, 1H). MS (ESI−) m/e 832 (M−H)−.

Workup

  1. filtrationit was filtered
  2. washthe filter-cake was washed with ethyl acetate
  3. additionThe flitrate was diluted with ethyl acetate (200 mL) and ether (50 mL)
  4. washit was washed (H2O×2, brine)
  5. dry with materialdried (MgSO4)
  6. customevaporated
  7. customto give a yellow glass
  8. temperaturethe mixture was heated
  9. temperatureto reflux under Ar for 18 h
  10. customThe cooled mixture was then evaporated to dryness
  11. washwashed (H2O×2, brine)
  12. dry with materialdried (MgSO4)
  13. customevaporated
  14. customThe resulting solid was chromatographed (SiO2/2-32% ethyl acetate-hexane)

Sources & evidence

ORD record
ord-adb6509a939148759712505c9c6a5a96
Source dataset
uspto-grants-2003_11
Patent number
US06653290B2

Reaction notes

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