Potassium Iodide → HCID 69019354, compound

HRID 1437915Notes

Reaction equation

HRID 1437915 reaction equation
[CH2:1](Br)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:9][C@@:10]12[C:27]([CH3:29])([CH3:28])[C@@H:13]([C:14]3[C:15](=[O:26])[N:16]([C:19]4[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][CH:20]=4)[NH:17][C:18]=31)[CH2:12][CH2:11]2.[I-].[K+].C(=O)([O-])[O-].[K+].[K+]>CN(C)C=O.O>[CH2:1]([N:17]1[C:18]2[C@@:10]3([CH3:9])[C:27]([CH3:29])([CH3:28])[C@H:13]([CH2:12][CH2:11]3)[C:14]=2[C:15](=[O:26])[N:16]1[C:19]1[CH:20]=[CH:21][C:22]([CH3:25])=[CH:23][CH:24]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH2:1]([O:26][C:15]1[N:16]([C:19]2[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][CH:20]=2)[N:17]=[C:18]2[C:14]=1[C@@H:13]1[C:27]([CH3:29])([CH3:28])[C@@:10]2([CH3:9])[CH2:11][CH2:12]1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 4875Potassium IodideHCID 7498Benzyl BromideHCID 11430Potassium CarbonateHCID 57941413HCID 57941413, compound2×

Product 2

HCID 57941437HCID 57941437, compoundYield 3.5%HCID 69019354HCID 69019354, compoundYield 53%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Benzyl bromide (0.18 mL, 1.5 mmol) was added to (4S,7R)-7,8,8-trimethyl-2-p-tolyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (Intermediate 9; 400 mg, 1.4 mmol), potassium iodide (34 mg, 0.14 mmol) and potassium carbonate (400 mg, 2.8 mmol) in dimethylformamide (5 mL). The mixture was heated at 80 degrees under argon overnight. The reaction mixture was diluted with water and extracted three times with ethyl acetate. The combined organic layers were washed with water and brine, dried (magnesium sulfate), filtered, evaporated, and purified using an Analogix Intelliflash 280 system (Analogix, Inc., Burlington, Wis.) with an RS-12 column, eluting with 0-65% ethyl acetate/hexanes to give (4S,7R)-1-benzyl-7,8,8-trimethyl-2-p-tolyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (19 mg, 3.5%) as an off-white solid and (4S,7R)-3-benzyloxy-7,8,8-trimethyl-2-p-tolyl-4,5,6,7-tetrahydro-2H-4,7-methano-indazole (279 mg, 53%) as a yellow oil. ES(+)-MS (M+H) 373.

Workup

  1. temperatureThe mixture was heated at 80 degrees under argon overnight
  2. extractionextracted three times with ethyl acetate
  3. washThe combined organic layers were washed with water and brine
  4. dry with materialdried (magnesium sulfate)
  5. filtrationfiltered
  6. customevaporated
  7. custompurified
  8. washeluting with 0-65% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-2521877c6690471fa6002db2c2d95b69
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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