Sodium Nitrite → HCID 86643146, compound

HRID 1094763Notes

Reaction equation

HRID 1094763 reaction equation
FC(F)(F)S(O)(=O)=O.[CH3:9][C:10]1([CH3:22])[N:14]([C:15](=[O:18])[CH2:16][NH2:17])[C@@H:13]([CH2:19][CH:20]=[CH2:21])[CH2:12][O:11]1.[N:23]([O-])=O.[Na+]>C(Cl)Cl.O>[N+:17](=[CH:16][C:15]([N:14]1[C@@H:13]([CH2:19][CH:20]=[CH2:21])[CH2:12][O:11][C:10]1([CH3:22])[CH3:9])=[O:18])=[N-:23]

Participants

5

Reactant 2

HCID 23668193Sodium NitriteHCID 86643145HCID 86643145, compound

Product 1

HCID 86643146HCID 86643146, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
2 °C

Procedure

{2-[(4S)-2,2-dimethyl-4-(2-propen-1-yl)-1,3-oxazolidin-3-yl]-2-oxoethyl}amine trifluoromethansulfonate D23 (67.0 g) was dissolved in DCM (670 ml) and pH=5 Buffer solution (670 ml) and cooled to 2° C. (internal). Sodium nitrite (26.5 g, 385 mmol) dissolved in water (134 ml) was added dropwise to the reaction mixture stirred at 2° C. over 30 min. The reaction mixture was stirred at 3° C. for 2.5 hours. Phases were separated. Water phase was back-extracted with DCM (1×670 ml, 1×335 ml). The combined organic layers, dried (Na2SO4), were evaporated (bath temperature 30° C.) to give 43 g of crude product. This crude was purified over silica pad [(230-400 Mesh) eluting with Cy/EtOAc 8/2, 7/3, 6/4] to give the title compound D24 (36.58 g) as pale yellow oil. UPLC (Acid GEN_QC): rt=0.59 minutes, peak observed: 210 (M+1) C10H15N3O2 requires 209. 1H NMR (400 MHz, CDCl3) δ ppm 1.58 (s, 3 H) 1.69 (s, 3 H) 2.25-2.50 (m, 2 H) 3.43-3.70 (m, 1 H) 3.82-4.01 (m, 2 H) 4.84 (s, 1 H) 5.09-5.24 (m, 2 H) 5.63-5.84 (m, 1 H)

Workup

  1. additionwas added dropwise to the reaction mixture
  2. stirringThe reaction mixture was stirred at 3° C. for 2.5 hours
  3. customPhases were separated
  4. extractionWater phase was back-extracted with DCM (1×670 ml, 1×335 ml)
  5. dry with materialThe combined organic layers, dried (Na2SO4)
  6. customwere evaporated (bath temperature 30° C.)
  7. customto give 43 g of crude product
  8. customThis crude was purified over silica pad [(230-400 Mesh) eluting with Cy/EtOAc 8/2, 7/3, 6/4]

Sources & evidence

ORD record
ord-8d358ce5d1024f84a5389daa3859f09f
Source dataset
uspto-grants-2012_03
Patent number
US08133908B2

Reaction notes

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