Iodoethane → Ethyl 4-(benzyloxycarbonylamino)bicyclo[2.2.2]octane-1-carboxylate

HRID 555674Notes

Reaction equation

HRID 555674 reaction equation
[CH2:1]([O:8][C:9]([NH:11][C:12]12[CH2:19][CH2:18][C:15]([C:20]([OH:22])=[O:21])([CH2:16][CH2:17]1)[CH2:14][CH2:13]2)=[O:10])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(=O)(O)[O-].[Na+].[CH2:28](I)[CH3:29]>CN(C)C=O>[CH2:1]([O:8][C:9]([NH:11][C:12]12[CH2:19][CH2:18][C:15]([C:20]([O:22][CH2:28][CH3:29])=[O:21])([CH2:16][CH2:17]1)[CH2:14][CH2:13]2)=[O:10])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 6340Iodoethane2×HCID 516892Sodium Bicarbonate2×HCID 106622014-(Benzyloxycarbonylamino)bicyclo[2.2.2]octane-1-carboxylic acid

Product 1

HCID 10616503Ethyl 4-(benzyloxycarbonylamino)bicyclo[2.2.2]octane-1-carboxylate

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
55 °C

Procedure

4-Benzyloxycarbonylaminobicyclo[2.2.2]octane-1-carboxylic acid (56.0 g) was dissolved in N,N-dimethylformamide (1000 mL). To this solution, sodium bicarbonate (46.6 g) and then ethyl iodide (22.2 mL) were added and the mixture was stirred at 50 to 60° C. for 5 hours. Subsequently, additional sodium bicarbonate (46.6 g) and ethyl iodide (22.2 mL) were added and the mixture was stirred for additional 3 hours. The insoluble materials in the mixture were filtered and the filtrate was concentrated under reduced pressure. The residue was dissolved in ethyl acetate (700 mL) and the solution was washed with water, dried over anhydrous sodium sulfate, and dried under reduced pressure. The resulting residue was purified by silica gel column chromatography (eluant:hexane:ethyl acetate=2:1→ethyl acetate) to give ethyl 4-benzyloxycarbonylamino-bicyclo[2.2.2]octane-1-carboxylate (56.8 g).

Workup

  1. stirringthe mixture was stirred for additional 3 hours
  2. filtrationThe insoluble materials in the mixture were filtered
  3. concentrationthe filtrate was concentrated under reduced pressure
  4. dissolutionThe residue was dissolved in ethyl acetate (700 mL)
  5. washthe solution was washed with water
  6. dry with materialdried over anhydrous sodium sulfate
  7. customdried under reduced pressure
  8. customThe resulting residue was purified by silica gel column chromatography (eluant:hexane:ethyl acetate=2:1→ethyl acetate)

Sources & evidence

ORD record
ord-a38c88ba70774c17966c50e895a4d7ac
Source dataset
uspto-grants-2011_11
Patent number
US08053465B2

Reaction notes

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