Toluene → Carbamic acid, [(1R,2S)-2-ethenylcyclopropyl]-, 1,1-dimethylethyl ester, rel-

HRID 582123Notes

Reaction equation

HRID 582123 reaction equation
C([N:3]([CH2:6]C)[CH2:4][CH3:5])C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:15])C=CC=CC=1.[C:25]([OH:29])([CH3:28])([CH3:27])[CH3:26].[C:30]1([CH3:36])C=CC=C[CH:31]=1>C(OCC)C>[C:25]([O:29][C:6]([NH:3][C@@H:4]1[CH2:5][C@H:36]1[CH:30]=[CH2:31])=[O:15])([CH3:28])([CH3:27])[CH3:26]

Participants

6

Reactant 4

HCID 1140Toluene3×HCID 6386tert-ButanolHCID 8471TriethylamineHCID 199401P,P-Diphenylphosphinic azide

Product 1

HCID 54277191Carbamic acid, [(1R,2S)-2-ethenylcyclopropyl]-, 1,1-dimethylethyl ester, rel-

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Procedure

The above acid (8.66 g, 77.43 mmol) was dissolved in anhydrous toluene (40 ml), cooled to 0°, treated with dry triethylamine (11.9 ml) and then, dropwise, with diphenylphosphoryl azide (23.4 g, Aldrich) in toluene (25 ml). The solution was warmed to 80° and kept at 80-85° for 45 mins. Anhydrous t-butanol (36 ml) and toluene (10 ml) were added quickly and the solution heated at 102° for 6 hours. The reaction mixture was allowed to cool and diluted with diethyl ether, washed with 1N orthophosphoric acid (100 ml), saturated aq.sodium bicarbonate and brine, dried and concentrated. The residual oil was purified by chromatography (silica: 350 g; hexane: ethyl acetate 95:5) to give the product as a colourless oil (3.91 g).

Workup

  1. temperaturecooled to 0°
  2. temperatureThe solution was warmed to 80°
  3. temperaturethe solution heated at 102° for 6 hours
  4. temperatureto cool
  5. washwashed with 1N orthophosphoric acid (100 ml)
  6. dry with materialsodium bicarbonate and brine, dried
  7. concentrationconcentrated
  8. customThe residual oil was purified by chromatography (silica: 350 g; hexane: ethyl acetate 95:5)

Sources & evidence

ORD record
ord-519bc35b4be242dd899280b2ad3ac313
Source dataset
uspto-grants-1999_07
Patent number
US05922748

Reaction notes

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