Methyl iodide → HCID 12339189, compound

HRID 1580143Notes

Reaction equation

HRID 1580143 reaction equation
[Li].[CH3:2]I.[CH3:4][O:5][C:6]1[CH:7]=[C:8]([C:12]23[CH2:27][CH:16]([N:17]([CH2:20][C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)[C:18]2=O)[CH2:15][CH2:14][CH2:13]3)[CH:9]=[CH:10][CH:11]=1.[BH4-].[Na+]>CCOCC.C1C=CC=CC=1.C(O)C.O>[CH3:4][O:5][C:6]1[CH:7]=[C:8]([C:12]23[CH2:27][CH:16]([N:17]([CH2:20][C:21]4[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=4)[CH:18]2[CH3:2])[CH2:15][CH2:14][CH2:13]3)[CH:9]=[CH:10][CH:11]=1

Participants

9

Reactant 4

HCID 6328Methyl iodideHCID 3028194LithiumHCID 4311764Sodium borohydrideHCID 12339188HCID 12339188, compound

Product 1

HCID 12339189HCID 12339189, compoundYield 39.3%

Reagents, catalysts & solvents 4

HCID 241BenzeneSolventHCID 702EthanolSolvent3×HCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

0.262 g of lithium is added to 10 ml of absolute ether in a nitrogen atmosphere, and a solution of 2.8 g of methyl iodide in 5 ml of absolute ether is added dropwise thereto at 0° to 5°C. The mixture is stirred at the same temperature for 50 minutes. Then, a solution of 1.5 g of 1-(3-methoxyphenyl)-6-benzyl-6-azabicyclo[3,2,1]octane- 7-one in 30 ml of absolute benzene is added dropwise to the mixture at 5° to 10°C in a nitrogen atmosphere. The mixture is stirred at room temperature overnight. After water is added to the mixture, the benzene-ether layer is washed with water, dried and then evaporated to remove solvent. The residue thus obtained is dissolved in 60 ml of ethanol, and 0.355 g of sodium borohydride is added to the ethanol solution at 8° to 10°C. The ethanol solution is stirred at room temperature for 2 hours. Then, the ethanol solution is concentrated under reduced pressure to remove solvent. water is added to the residue, and the aqueous mixture is extracted with ether. The ether extract is extracted with 10% aqueous hydrochloric acid. The aqueous extract is washed with ether, made alkaline with ammonia and again extracted with ether. The ether extract thus obtained is dried and evaporated to remove solvent. The residue is dissolved in 5 ml of chloroform. The chloroform solution is poured onto a column of 100 g of silica gel. Then, the column is eluted with a mixture of 2850 ml of chloroform and 150 ml of methanol. The effluent obtained is evaporated to remove solvent, whereby 0.59 g of 1-(3-methoxyphenyl)-6-benzyl-7-methyl-6-azabicyclo[3,2,1]octane is obtained. Picrate: M.p. 184°-186°C(recrystallized from methanol).

Workup

  1. customat 0° to 5°C
  2. stirringThe mixture is stirred at room temperature overnight
  3. washthe benzene-ether layer is washed with water
  4. customdried
  5. customevaporated
  6. customto remove solvent
  7. customThe residue thus obtained
  8. concentrationThen, the ethanol solution is concentrated under reduced pressure
  9. customto remove solvent
  10. additionwater is added to the residue
  11. extractionthe aqueous mixture is extracted with ether
  12. extractionThe ether extract
  13. extractionis extracted with 10% aqueous hydrochloric acid
  14. extractionThe aqueous extract
  15. washis washed with ether
  16. extractionagain extracted with ether
  17. extractionThe ether extract thus
  18. customobtained
  19. customis dried
  20. customevaporated
  21. customto remove solvent
  22. dissolutionThe residue is dissolved in 5 ml of chloroform
  23. additionThe chloroform solution is poured onto a column of 100 g of silica gel
  24. washThen, the column is eluted with a mixture of 2850 ml of chloroform and 150 ml of methanol
  25. customThe effluent obtained
  26. customis evaporated
  27. customto remove solvent

Sources & evidence

ORD record
ord-1b0d84a15655481bb8ca7f4902efee1c
Source dataset
uspto-grants-1976_01
Patent number
US03932429

Reaction notes

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