Sodium Sulfite → HCID 89601340, compound

HRID 570914Notes

Reaction equation

HRID 570914 reaction equation
[C:1]([NH:4][N:5]1[CH2:10][C:9]([CH:11]([OH:13])[CH3:12])=[N:8][N:7]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[C:6]1=[O:21])(=[O:3])[CH3:2].C([O-])(O)=O.[Na+].[Na+].[Br-].[O-]Cl.[Na+].[O-]S([O-])=O.[Na+].[Na+]>C(OCC)(=O)C.O>[C:1]([NH:4][N:5]1[CH2:10][C:9]([C:11](=[O:13])[CH3:12])=[N:8][N:7]([C:14]([O:16][C:17]([CH3:20])([CH3:19])[CH3:18])=[O:15])[C:6]1=[O:21])(=[O:3])[CH3:2]

Participants

8

Reactant 5

HCID 24437Sodium Sulfite2×HCID 253881Sodium BromideHCID 516892Sodium BicarbonateHCID 23665760Sodium HypochloriteHCID 89602037HCID 89602037, compound

Product 1

HCID 89601340HCID 89601340, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of tert-butyl 4-acetamido-6-(1-hydroxyethyl)-3-oxo-5H-1,2,4-triazine-2-carboxylate (601 mg, 1.50 mmol) in ethyl acetate (3.9 mL) was added a solution of NaHCO3 (378 mg, 4.50 mmol) and NaBr (170 mg, 1.65 mmol) in water (2.6 mL). After cooling of the biphasic mixture to 0° C., 2,2,6,6-Tetramethyl-piperidin-1-yl)oxyl (“TEMPO”) (12.0 mg, 0.0750 mmol) was added in one portion followed by dropwise addition of NaOCl (6 wt % in water, 2.79 mL, 2.25 mmol) to the vigorously stirred solution. After completion of the addition, stirring at 0° C. was continued for 30 min. Subsequently, a solution of aqueous Na2SO3 was added until the reaction mixture had completely discolored. Additional solid Na2SO3 was added to saturate the aqueous phase. The mixture was transferred to a separation funnel and the layers were separated. The organic layer was washed with brine (100 mL), dried (Na2SO4), filtered and concentrated under reduced pressure. LCMS (Method I) RT 1.42 min. [(M-Boc)+Na]+ 221.

Workup

  1. addition2,2,6,6-Tetramethyl-piperidin-1-yl)oxyl (“TEMPO”) (12.0 mg, 0.0750 mmol) was added in one portion
  2. additionAfter completion of the addition
  3. concentrationto saturate the aqueous phase
  4. customThe mixture was transferred to a separation funnel
  5. customthe layers were separated
  6. washThe organic layer was washed with brine (100 mL)
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customLCMS (Method I) RT 1.42 min. [(M-Boc)+Na]+ 221

Sources & evidence

ORD record
ord-67a8bb3ea1924f118c80266c7e2b0406
Source dataset
uspto-grants-2015_05
Patent number
US09024019B2

Reaction notes

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