Dimethyl Sulfate → HCID 57941367, compound

HRID 1437920Notes

Reaction equation

HRID 1437920 reaction equation
S(OC)(O[CH3:5])(=O)=O.[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([N:15]2[C:23](=[O:24])[C:22]3[C@@H:21]4[C:25]([CH3:27])([CH3:26])[C@@:18]([CH3:28])([CH2:19][CH2:20]4)[C:17]=3[NH:16]2)=[CH:11][CH:10]=1>[OH-].[Na+]>[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([N:15]2[C:23](=[O:24])[C:22]3[C@@H:21]4[C:25]([CH3:27])([CH3:26])[C@@:18]([CH3:28])([CH2:19][CH2:20]4)[C:17]=3[N:16]2[CH3:5])=[CH:11][CH:10]=1

Participants

4

Reactant 2

HCID 6497Dimethyl SulfateHCID 57941492HCID 57941492, compound2×

Product 1

HCID 57941367HCID 57941367, compoundYield 7%

Reagents, catalysts & solvents 1

HCID 14798Sodium HydroxideSolvent

Procedure

Dimethyl sulfate (84 μL, 0.92 mmol) was added to a solution of (4S,7R)-2-(4-chloro-phenyl)-7,8,8-trimethyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (Intermediate 11; 252 mg, 0.83 mmol) in 1 M NaOH (3 mL) and the resulting solution was stirred at room temperature overnight. The aqueous supernatant was decanted away from the red gum, and the gum was dissolved in ethyl acetate. This solution was washed with water, dried (sodium sulfate), filtered, evaporated, and purified by chromatography using a Waters Sep-Pak® column, eluting with 20% ethyl acetate/hexanes to elute 2-(4-chloro-phenyl)-3-methoxy-7,8,8-trimethyl-4,5,6,7-tetrahydro-2H-4,7-methano-indazole, and then a step gradient of 50% ethyl acetate/hexanes, 66% ethyl acetate/hexanes, and finally 4% methanol/ethyl acetate to give (4S,7R)-2-(4-chloro-phenyl)-1,7,8,8-tetramethyl-1,2,4,5,6,7-hexahydro-4,7-methano-indazol-3-one (18 mg, 7%). ES(+)-MS (M+H) 317.

Workup

  1. customThe aqueous supernatant was decanted away from the red gum
  2. dissolutionthe gum was dissolved in ethyl acetate
  3. washThis solution was washed with water
  4. dry with materialdried (sodium sulfate)
  5. filtrationfiltered
  6. customevaporated
  7. custompurified by chromatography
  8. washeluting with 20% ethyl acetate/hexanes
  9. washto elute 2-(4-chloro-phenyl)-3-methoxy-7,8,8-trimethyl-4,5,6,7-tetrahydro-2H-4,7-methano-indazole

Sources & evidence

ORD record
ord-df2ff62f3613416aacfc6c036e45b190
Source dataset
uspto-grants-2009_11
Patent number
US07622492B2

Reaction notes

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