Water → Ethyl 3-(4-tert-butoxycarbonylaminocyclohex-1-enyl)benzoate

HRID 1425296Notes

Reaction equation

HRID 1425296 reaction equation
OC1CCC([C:8]2[CH:18]=[CH:17][CH:16]=[CH:15][C:9]=2[C:10]([O:12][CH2:13][CH3:14])=[O:11])=CC1.CS(Cl)(=O)=O.[N-]=[N+]=[N-].[Na+].O.[C:29]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(O[C:56]([O:58][C:59]([CH3:62])([CH3:61])[CH3:60])=[O:57])(OC(C)(C)C)=O.[N:63]1[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=1>C(OCC)(=O)C>[C:59]([O:58][C:56]([NH:63][CH:68]1[CH2:67][CH2:66][C:65]([C:18]2[CH:8]=[C:9]([CH:15]=[CH:16][CH:17]=2)[C:10]([O:12][CH2:13][CH3:14])=[O:11])=[CH:64][CH2:29]1)=[O:57])([CH3:60])([CH3:61])[CH3:62]

Participants

9

Reactant 7

HCID 962WaterHCID 1049PyridineHCID 11776TriphenylphosphineHCID 31297Methanesulfonyl chlorideHCID 33557Sodium AzideHCID 90495Di-tert-butyl dicarbonateHCID 86648765HCID 86648765, compound

Product 1

HCID 67548489Ethyl 3-(4-tert-butoxycarbonylaminocyclohex-1-enyl)benzoate

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of ethyl (4-hydroxycyclohex-1-enyl)benzoate obtained in Example (195a) (1 g, 4.06 mmol) in pyridine (20 mL) was cooled to 0° C. Methanesulfonyl chloride (628 μL, 8.12 mmol) was added at the same temperature, and the mixture was stirred at 0° C. for two hours. The reaction solution was diluted with ethyl acetate, washed with 1 N hydrochloric acid and brine, and dried over magnesium sulfate. Thereafter, the solvent was evaporated under reduced pressure. The resulting residue was dissolved in N,N-dimethylformamide (30 mL). Sodium azide (1.32 g, 20.3 mmol) was added at room temperature, and the mixture was stirred at 70° C. for 18 hours. The reaction solution was diluted with ethyl acetate, washed with brine, and dried over magnesium sulfate. Thereafter, the solvent was evaporated under reduced pressure. The resulting residue was dissolved in tetrahydrofuran (30 mL). Water (109 μL, 6.09 mmol) and triphenylphosphine (1.17 g, 4.47 mmol) were added at room temperature, and the mixture was stirred at room temperature for 18 hours. After 18 hours, di-tert-butyl dicarbonate (975 mg, 4.47 mmol) was added, and the mixture was stirred at room temperature for five hours. The reaction solution was diluted with ethyl acetate, washed with brine, and dried over magnesium sulfate. Thereafter, the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (elution solvent: hexane/ethyl acetate=2/1) to obtain 510 g of the title compound as a yellow oily substance (32%).

Workup

  1. washwashed with 1 N hydrochloric acid and brine
  2. dry with materialdried over magnesium sulfate
  3. customThereafter, the solvent was evaporated under reduced pressure
  4. dissolutionThe resulting residue was dissolved in N,N-dimethylformamide (30 mL)
  5. stirringthe mixture was stirred at 70° C. for 18 hours
  6. washwashed with brine
  7. dry with materialdried over magnesium sulfate
  8. customThereafter, the solvent was evaporated under reduced pressure
  9. dissolutionThe resulting residue was dissolved in tetrahydrofuran (30 mL)
  10. stirringthe mixture was stirred at room temperature for 18 hours
  11. waitAfter 18 hours
  12. stirringthe mixture was stirred at room temperature for five hours
  13. washwashed with brine
  14. dry with materialdried over magnesium sulfate
  15. customThereafter, the solvent was evaporated under reduced pressure
  16. customThe resulting residue was purified by silica gel column chromatography (elution solvent: hexane/ethyl acetate=2/1)

Sources & evidence

ORD record
ord-a70e16776c194090acf6d6b92aef5180
Source dataset
uspto-grants-2015_01
Patent number
US08927588B2

Reaction notes

Loading…