tert-Butanol → (2-Phenylhexahydro-2,5-methanopentalen-3a-yl)carbamic acid tert-butyl ester

HRID 2405697Notes

Reaction equation

HRID 2405697 reaction equation
[C:1]1([C:7]23[CH2:18][CH:11]4[CH2:12][C:13](C(O)=O)([CH2:14]2)[CH:9]([CH2:10]4)[CH2:8]3)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([N:21]([CH2:24]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:33])C=CC=CC=1.[C:43]([OH:47])([CH3:46])([CH3:45])[CH3:44]>>[C:43]([O:47][C:24](=[O:33])[NH:21][C:13]12[CH2:12][CH:11]3[CH2:18][C:7]([C:1]4[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=4)([CH2:8][CH:9]1[CH2:10]3)[CH2:14]2)([CH3:46])([CH3:45])[CH3:44]

Participants

5

Reactant 4

HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 673007182-Phenylhexahydro-2,5-methanopentalene-3a-carboxylic acid

Product 1

HCID 68310785(2-Phenylhexahydro-2,5-methanopentalen-3a-yl)carbamic acid tert-butyl ester

Procedure

2-Phenylhexahydro-2,5-methanopentalen-3a-carboxylic acid (50 g) was dissolved in t-butanol (1 l), and triethylamine (51 g) was added to this solution. Diphenylphosphoryl azide (56 g) was added in portions at room temperature. The reaction was stirred first at room temperature and then at reflux. After removal of the t-butanol, the residue was taken up in water (800 ml). The precipitated solids were filtered off and washed repeatedly with water. After drying under reduced pressure, the solids were taken up in tert-butyl methyl ether. This forms a solid, which was filtered off. The filtrate was concentrated fully under reduced pressure and then stirred with diisopropyl ether. The solids were filtered off with suction and washed with a mixture of diisopropyl ether and n-heptane. After drying, (2-phenylhexahydro-2,5-methanopentalen-3a-yl)carbamic acid tert-butyl ester (83.9 g) was obtained.

Workup

  1. temperatureat reflux
  2. customAfter removal of the t-butanol
  3. filtrationThe precipitated solids were filtered off
  4. washwashed repeatedly with water
  5. customAfter drying under reduced pressure
  6. filtrationwas filtered off
  7. concentrationThe filtrate was concentrated fully under reduced pressure
  8. stirringstirred with diisopropyl ether
  9. filtrationThe solids were filtered off with suction
  10. washwashed with a mixture of diisopropyl ether and n-heptane
  11. customAfter drying

Sources & evidence

ORD record
ord-dcffcaa412e44302bafbdc115a0624c7
Source dataset
uspto-grants-2014_08
Patent number
US08809324B2

Reaction notes

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