Triethylamine → HCID 131721338, compound

HRID 1585230Notes

Reaction equation

HRID 1585230 reaction equation
C([N:3]([CH2:6]C)CC)C.ClC(OCC)=[O:10].[CH3:14][O:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[CH2:22][C:23]([CH:25]1[CH:33]2[C:28](C(O)=O)([CH2:29][C:30]3[CH:43]=[CH:42][CH:41]=[CH:40][C:31]=3[CH:32]2[C:34]2[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=2)[CH2:27][NH:26]1)=[O:24].[N-]=[N+]=[N-].[Na+]>CC(C)=O.O>[N-:3]=[C:6]=[O:10].[CH3:14][O:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[CH2:22][C:23]([CH:25]1[CH:33]2[CH:28]([CH2:29][C:30]3[CH:43]=[CH:42][CH:41]=[CH:40][C:31]=3[CH:32]2[C:34]2[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=2)[CH2:27][NH:26]1)=[O:24]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 10928Ethyl chloroformateHCID 33557Sodium AzideHCID 86754402HCID 86754402, compound

Product 1

HCID 131721338HCID 131721338, compound

Reagents, catalysts & solvents 2

HCID 180AcetoneSolvent2×HCID 962WaterSolvent3×

Conditions

Temperature
2.5 °C

Procedure

0.9 g (8.9 mmol) of triethylamine and 1.085 g (10 mmol) of ethyl chloroformate in solution in 40 cm3 of acetone are successively added to a solution of 3.43 g (7.4 mmol) of (3aRS, 4SR, 9SR, 9aRS)-4,9-ethano-2-(2-methoxyphenyl)acetyl-9-phenyl-2,3,3a,4,9,9a-hexahydro-1H-benzo[f]isoindole-3a-carboxylic acid in 20 cm3 of acetone and 6 cm3 of water, which solution has been cooled to 0-2° C. and maintained under a nitrogen atmosphere. After stirring for 30 minutes at 0-5° C., a solution of 0.77 g (7.4 mmol) of sodium azide in 15 cm3 of water is added dropwise and stirring is then maintained at 0-5° C. for 1 hour. The reaction mixture is then poured into 200 cm3 of water and the acylazide is extracted with 5 times 40 cm3 of ethyl ether. The combined organic phases are washed with water and then dried over magnesium sulphate. After evaporating the ether under reduced pressure, 50 cm3 of toluene are added. The mixture is then gradually heated to 85-90° C. and then at reflux for 1 hour after gas evolution has ceased. The crystals formed on cooling are filtered off and then washed with petroleum ether. 2.98 g (88%) of (3aRS, 4SR, 9SR, 9aRS)-4,9-ethano-3a-isocyanate-2-(2-methoxyphenyl)acetyl-9-phenyl-2,3,3a,4,9,9a-hexahydro-1H-benzo[f]isoindole are thus obtained in the form of a white powder, the characteristics of which are as follows: melting point=185° C., mass spectrum (E.I.) M/Z=464 (M+)

Workup

  1. temperaturemaintained under a nitrogen atmosphere
  2. stirringstirring
  3. temperatureis then maintained at 0-5° C. for 1 hour
  4. extractionthe acylazide is extracted with 5 times 40 cm3 of ethyl ether
  5. washThe combined organic phases are washed with water
  6. dry with materialdried over magnesium sulphate
  7. customAfter evaporating the ether under reduced pressure, 50 cm3 of toluene
  8. additionare added
  9. temperatureThe mixture is then gradually heated to 85-90° C.
  10. temperatureat reflux for 1 hour after gas evolution
  11. customThe crystals formed
  12. temperatureon cooling
  13. filtrationare filtered off
  14. washwashed with petroleum ether

Sources & evidence

ORD record
ord-b07b035751fb43119708e9ff8d4d5d70
Source dataset
uspto-grants-1999_08
Patent number
US05936097

Reaction notes

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