Triethylamine → HCID 59688509, compound

HRID 2267622Notes

Reaction equation

HRID 2267622 reaction equation
C(N(CC)CC)C.O[C@H:9]1[C:15](=[O:16])[NH:14][C:13]2[CH:17]=[CH:18][CH:19]=[CH:20][C:12]=2[O:11][C@@H:10]1[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.FC(F)(F)S(Cl)(=O)=O.[N-:35]=[N+:36]=[N-:37].[Na+]>ClCCl.O.CN(C=O)C>[N:35]([C@@H:9]1[C:15](=[O:16])[NH:14][C:13]2[CH:17]=[CH:18][CH:19]=[CH:20][C:12]=2[O:11][C@@H:10]1[C:21]1[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1)=[N+:36]=[N-:37]

Participants

8

Reactant 4

HCID 8471Triethylamine3×HCID 33557Sodium AzideHCID 79000Trifluoromethanesulfonyl chloride3×HCID 58997949HCID 58997949, compound

Product 1

HCID 59688509HCID 59688509, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 6344DichloromethaneSolvent

Procedure

Triethylamine (1.667 g, 16.472 mmol) was added via syringe to a stirred solution of (2R,3R)-3-hydroxy-2-phenyl-2,3-dihydro-1,5-benzoxazepin-4(5H)-one (64c) (2.532 g, 9.922 mmol) in dichloromethane (90 mL) under nitrogen at −40° C. Next trifluoromethanesulfonyl chloride (2.541 g, 15.080 mmol) was added slowly via syringe and the mixture kept at −25° C. for 2 h. Additional triethylamine (1.667 g, 16.472 mmol) was added followed by trifluoromethanesulfonyl chloride (2.541 g, 15.080 mmol) and the reaction was kept for 8 h at −25° C. Again, additional triethylamine (1.667 g, 16.472 mmol) was added via syringe followed by trifluoromethanesulfonyl chloride (2.541 g, 15.080 mmol) and the reaction was kept for 24 h at −25° C. The solvent was evaporated without heating under reduced pressure and the residue dissolved in DMF (25 mL). Sodium azide (3.000 g, 46.15 mmol) was added to the stirred DMF solution at −10° C. and the reaction was allowed to warm to ambient temperature. After 2 h the reaction was diluted with water (300 mL) and extracted three times with ethyl acetate. The combined organic extracts were washed with saturated aqueous sodium bicarbonate and then with brine. The organic solution was dried, filtered and evaporated. The residue was purified by flash chromatography an silica gel eluting with 30:1 (v/v) dichloromethane: ethyl acetate to afford the title compound as an off-white solid. TLC Rf=0.35 (20:1 (v/v) dichloromethane: ethyl acetate). 1H NMR (300 MHz, CDCl3) δ4.45 (d, 1H, J=6 Hz), 5.56 (d, 1H, J=6 Hz), 7.00-7.07 (m, 1H), 7.10-7.26 (m, 3H), 7.40-7.46 (m, 3H), 7.51-7.61 (m, 3H). MS APCI, m/z=253 (M+1-N2). LC/MS: 2.25 min. [α]D25=−179° (c=5.0, CHCl3)

Workup

  1. waitthe reaction was kept for 8 h at −25° C
  2. waitthe reaction was kept for 24 h at −25° C
  3. customThe solvent was evaporated
  4. temperaturewithout heating under reduced pressure
  5. dissolutionthe residue dissolved in DMF (25 mL)
  6. extractionextracted three times with ethyl acetate
  7. washThe combined organic extracts were washed with saturated aqueous sodium bicarbonate
  8. customThe organic solution was dried
  9. filtrationfiltered
  10. customevaporated
  11. customThe residue was purified by flash chromatography an silica gel eluting with 30:1 (v/v) dichloromethane

Sources & evidence

ORD record
ord-d03ca3531ed54d12b1353a32c27bca3b
Source dataset
uspto-grants-2010_12
Patent number
US07858776B2

Reaction notes

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