Dimethyl Sulfate → HCID 69021044, compound

HRID 1437913Notes

Reaction equation

HRID 1437913 reaction equation
[CH3:1][C@@:2]12[C:19]([CH3:21])([CH3:20])[C@@H:5]([C:6]3[C:7](=[O:18])[N:8]([C:11]4[CH:16]=[CH:15][C:14]([CH3:17])=[CH:13][CH:12]=4)[NH:9][C:10]=31)[CH2:4][CH2:3]2.S(OC)(O[CH3:26])(=O)=O>[OH-].[Na+].O>[CH3:26][N:9]1[C:10]2[C@@:2]3([CH3:1])[C:19]([CH3:21])([CH3:20])[C@H:5]([CH2:4][CH2:3]3)[C:6]=2[C:7](=[O:18])[N:8]1[C:11]1[CH:16]=[CH:15][C:14]([CH3:17])=[CH:13][CH:12]=1.[CH3:26][O:18][C:7]1[N:8]([C:11]2[CH:16]=[CH:15][C:14]([CH3:17])=[CH:13][CH:12]=2)[N:9]=[C:10]2[C:6]=1[C@@H:5]1[C:19]([CH3:21])([CH3:20])[C@@:2]2([CH3:1])[CH2:3][CH2:4]1

Participants

6

Reactant 2

HCID 6497Dimethyl SulfateHCID 57941413HCID 57941413, compound2×

Product 2

HCID 57941391HCID 57941391, compoundYield 20%HCID 69021044HCID 69021044, compoundYield 32%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 14798Sodium HydroxideSolvent

Procedure

(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) was dissolved in 1 M NaOH (5 mL) and dimethyl sulfate (0.14 mL, 1.46 mmol) was added. The mixture was stirred at room temperature overnight and then 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 0-100% ethyl acetate/hexanes to give (4S,7R)-1,7,8,8-tetramethyl-2-p-tolyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (82 mg, 20%) as an off-white solid and (4S,7R)-3-methoxy-7,8,8-trimethyl-2-p-tolyl-4,5,6,7-tetrahydro-2H-4,7-methano-indazole (134 mg, 32%) as a yellow solid. ES(+)-MS (M+H) 297.

Workup

  1. extractionextracted three times with ethyl acetate
  2. washThe combined organic layers were washed with water and brine
  3. dry with materialdried (magnesium sulfate)
  4. filtrationfiltered
  5. customevaporated
  6. custompurified
  7. washeluting with 0-100% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-05fc56b75ee246e198ca4c1279c68026
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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