Benzyl Alcohol → Methyl 4-{[(benzyloxy)carbonyl]amino}bicyclo[2.2.2]octane-1-carboxylate

HRID 227929Notes

Reaction equation

HRID 227929 reaction equation
[C:1]12([C:12]([O:14][CH3:15])=[O:13])[CH2:8][CH2:7][C:4](C(O)=O)([CH2:5][CH2:6]1)[CH2:3][CH2:2]2.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:23])C=CC=CC=1.C([N:35]([CH2:38]C)CC)C.[CH2:40]([OH:47])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1>C1(C)C=CC=CC=1>[CH2:40]([O:47][C:38]([NH:35][C:4]12[CH2:3][CH2:2][C:1]([C:12]([O:14][CH3:15])=[O:13])([CH2:6][CH2:5]1)[CH2:8][CH2:7]2)=[O:23])[C:41]1[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=1

Participants

6

Reactant 4

HCID 244Benzyl AlcoholHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 110420624-(Methoxycarbonyl)bicyclo[2.2.2]octane-1-carboxylic acid

Product 1

HCID 23149677Methyl 4-{[(benzyloxy)carbonyl]amino}bicyclo[2.2.2]octane-1-carboxylate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

Methyl hydrogen bicyclo[2.2.2]octane-1,4-dicarboxylate (25.0 g), diphenylphosphoryl azide (32.5 g), triethylamine (17.3 mL) and toluene (500 mL) were mixed together. The mixture was stirred for 2 hours at room temperature and was refluxed for 2 hours. To the resulting mixture, benzylalcohol (122 mL) was added and the mixture was further refluxed for 17 hours. Subsequently, the mixture was allowed to cool and was sequentially washed with a 10% aqueous citric acid, saturated aqueous solution of sodium bicarbonate and saturated brine. The mixture was then dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluant:hexane:ethyl acetate=2:1) to give methyl 4-benzyloxycarbonylaminobicyclo[2.2.2]octane-1-carboxylate (32.2 g).

Workup

  1. temperaturewas refluxed for 2 hours
  2. temperaturethe mixture was further refluxed for 17 hours
  3. temperatureto cool
  4. washwas sequentially washed with a 10% aqueous citric acid, saturated aqueous solution of sodium bicarbonate and saturated brine
  5. dry with materialThe mixture was then dried over anhydrous sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by silica gel column chromatography (eluant:hexane:ethyl acetate=2:1)

Sources & evidence

ORD record
ord-3346572df3644c17b79fdbde7cd4c69d
Source dataset
uspto-grants-2009_07
Patent number
US07560569B2

Reaction notes

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