Methyl iodide → HCID 12113746, compound

HRID 734179Notes

Reaction equation

HRID 734179 reaction equation
CI.[CH3:3][C:4]([CH3:48])=[CH:5][CH2:6][CH2:7][C@@:8]1([CH3:47])[O:17][C:16]2[C:15]([CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])=[C:14]3[O:23][C@@:24]45[C@@:34]6([CH2:39]/[CH:40]=[C:41](\[C:43]([OH:45])=[O:44])/[CH3:42])[O:35][C:36]([CH3:38])([CH3:37])[C@@H:25]4[CH2:26][C@H:27]([C:32]6=[O:33])[CH:28]=[C:29]5[C:30](=[O:31])[C:13]3=[C:12]([OH:46])[C:11]=2[CH:10]=[CH:9]1.N12CCCN=C1CCCC[CH2:50]2>CN(C)C=O.[Cl-].[Na+].O>[CH3:3][C:4]([CH3:48])=[CH:5][CH2:6][CH2:7][C@@:8]1([CH3:47])[O:17][C:16]2[C:11](=[C:12]([OH:46])[C:13]3[C:30](=[O:31])[C:29]4[C@@:24]5([C@@:34]6([CH2:39]/[CH:40]=[C:41](\[C:43]([O:45][CH3:50])=[O:44])/[CH3:42])[O:35][C:36]([CH3:37])([CH3:38])[C@@H:25]5[CH2:26][C@H:27]([C:32]6=[O:33])[CH:28]=4)[O:23][C:14]=3[C:15]=2[CH2:18][CH:19]=[C:20]([CH3:21])[CH3:22])[CH:10]=[CH:9]1

Participants

6

Reactant 3

HCID 6328Methyl iodideHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 9852185Gambogic acid

Product 1

HCID 12113746HCID 12113746, compoundYield 69%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolvent2×HCID 57417360Sodium chloride; waterSolvent

Procedure

A solution of methyl iodide (29 μL, 0.477 mmol) in 1.0 mL of N,N-dimethylformamide was added to a solution of gambogic acid (0.200 g, 0.318 mmol) and 1,8-diazabicyclo[5.4.0]undec-7-ene (47.6 μL, 0.318 mmol) in 0.2 mL of N,N-dimethylformamide and the mixture was stirred at room temperature for 3 h. The reaction mixture was poured into brine (30 mL) and was extracted with methylene chloride. The organic layer was wash with brine (2×30 mL) and the combined organic extracts were dried over MgSO4 and concentrated in vacuo to give the crude product. It was purified by column chromatography (18×2 cm column, SiO2, EtOAc/Hexane 1:5) to afford the methyl gambogate as an orange solid (0.14 g, 69 %). 1H NMR (CDCl3): 12.85 (s, 1H), 7.54 (d, J=6.9 Hz, 1H), 6.67 (d, J=10.5 Hz, 1H), 5.94 (t, J=6 Hz, 1H), 5.43 (d, J=10.2 Hz, 1H), 5.05 (m, 2H), 3.49 (m, 1H), 3.43 (s, 3H), 3.35-3.10 (s, 2H), 3.00 (t, J=7.2 Hz, 1H), 2.52 (d, J=10.2 Hz, 1H), 2.32 (quar, J=4.8 Hz, 1H), 2.02 (m, 1H), 1.74 (s, 3H), 1.69 (s, 3H), 1.67-1.64 (m, 9H), 1.55 (s, 3H), 1.44 (s, 3H), 1.29 (s, 3H).

Workup

  1. extractionwas extracted with methylene chloride
  2. washThe organic layer was wash with brine (2×30 mL)
  3. dry with materialthe combined organic extracts were dried over MgSO4
  4. concentrationconcentrated in vacuo
  5. customto give the crude product
  6. customIt was purified by column chromatography (18×2 cm column, SiO2, EtOAc/Hexane 1:5)

Sources & evidence

ORD record
ord-ebfc479f3c824f7aba37c2a5581be0bf
Source dataset
uspto-grants-2009_09
Patent number
US07592143B2

Reaction notes

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