Ethyl chloroformate → HCID 22618795, compound

HRID 842288Notes

Reaction equation

HRID 842288 reaction equation
Cl[C:2]([O:4][CH2:5]C)=[O:3].C(O[C:10]([CH2:35][CH3:36])([C:14](=C=O)[CH2:15][C:16]1[CH:21]=[CH:20][C:19]([O:22][CH2:23][CH2:24][CH2:25][CH2:26][C:27]2[CH:32]=[CH:31][CH:30]=[CH:29][CH:28]=2)=[CH:18][CH:17]=1)[C:11]([OH:13])=[O:12])C.[N-:37]=[N+]=[N-].[Na+].O.[C:42]1([CH3:52])C=CC(S(O)(=O)=O)=CC=1>CC(C)=O.O.C1C=CC=CC=1.CO.C(N(CC)CC)C>[CH2:35]([C:10]([NH:37][C:2]([O:4][CH3:5])=[O:3])([CH2:14][CH2:15][C:16]1[CH:17]=[CH:18][C:19]([O:22][CH2:23][CH2:24][CH2:25][CH2:26][C:27]2[CH:28]=[CH:29][CH:30]=[CH:31][CH:32]=2)=[CH:20][CH:21]=1)[C:11]([O:13][CH2:42][CH3:52])=[O:12])[CH3:36]

Participants

10

Reactant 4

HCID 10928Ethyl chloroformateHCID 33557Sodium AzideHCID 521998p-Toluenesulfonic acid monohydrateHCID 86754452HCID 86754452, compound

Product 1

HCID 22618795HCID 22618795, compound

Reagents, catalysts & solvents 5

HCID 180AcetoneSolventHCID 241BenzeneSolventHCID 887MethanolSolventHCID 962WaterSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
0 °C

Procedure

Ethyl chloroformate (7.4 g) was added to a solution of 2-ethoxy-carbonyl-2-ethyl-4-(4-(4-phenylbutyloxy)phenyl)butanoic acid (23 g) and triethylamine (9.5 ml) in acetone (224 ml) at 0° and the mixture was stirred at 0° C. for 70 minutes. A solution of sodium azide (4.4 g) in water (30 ml) was added thereto and the whole mixture was stirred at 0° C. for 45 minutes. The reaction mixture was poured into ice-water and extracted with ethyl acetate. The ethyl acetate layer was washed with water and a saturated brine, dried over anhydrous magnesium sulfate and the solvent was distilled away under reduced pressure. The residue obtained was dissolved in benzene (200 ml) and the solution was refluxed under heating for 70 minutes. Methanol (50 ml) and p-toluenesulfonic acid monohydrate (catalytic amount) were added to the solution. The mixture was further refluxed under heating for 10 minutes and allowed to stand at room temperature overnight. The solvent was distilled away and the residue obtained was purified by silica gel column chromatography (eluent; ethyl acetate:n-hexane=1:4) to give the subject compound (5.7 g).

Workup

  1. stirringthe whole mixture was stirred at 0° C. for 45 minutes
  2. extractionextracted with ethyl acetate
  3. washThe ethyl acetate layer was washed with water
  4. dry with materiala saturated brine, dried over anhydrous magnesium sulfate
  5. distillationthe solvent was distilled away under reduced pressure
  6. customThe residue obtained
  7. temperaturethe solution was refluxed
  8. temperatureunder heating for 70 minutes
  9. temperatureThe mixture was further refluxed
  10. temperatureunder heating for 10 minutes
  11. waitto stand at room temperature overnight
  12. distillationThe solvent was distilled away
  13. customthe residue obtained
  14. customwas purified by silica gel column chromatography (eluent; ethyl acetate:n-hexane=1:4)

Sources & evidence

ORD record
ord-0ba0977e903f4979a7b418a138e53657
Source dataset
uspto-grants-2002_04
Patent number
US06372800B1

Reaction notes

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