(Bis(2-methoxyethyl)amino)sulfur trifluoride → HCID 89456669, compound

HRID 1915784Notes

Reaction equation

HRID 1915784 reaction equation
O[C:2]1([CH3:25])[CH2:8][N:7]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:6][CH2:5][N:4]([C:16]2[N:20]([CH3:21])[N:19]=[CH:18][C:17]=2[N+:22]([O-:24])=[O:23])[CH2:3]1.COCCN(S(F)(F)[F:36])CCOC>C(Cl)Cl.C1COCC1>[F:36][C:2]1([CH3:25])[CH2:8][N:7]([C:9]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])[CH2:6][CH2:5][N:4]([C:16]2[N:20]([CH3:21])[N:19]=[CH:18][C:17]=2[N+:22]([O-:24])=[O:23])[CH2:3]1

Participants

5

Reactant 2

HCID 2734690(Bis(2-methoxyethyl)amino)sulfur trifluorideHCID 86680093HCID 86680093, compound

Product 1

HCID 89456669HCID 89456669, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolvent2×HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of tert-butyl 6-hydroxy-6-methyl-4-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,4-diazepane-1-carboxylate (100 mg, 0.28 mmol) in DCM (5 mL) was added deoxo-Fluor® (50% in THF, 0.26 mL, 0.7 mmol) and the mixture was stirred at room temperature for 18 hr. The mixture was diluted with DCM (30 mL), cooled in an ice water bath and quenched by dropwise addition of saturated aqueous NaHCO3 (40 mL). The resulting mixture was stirred for 10 min. The organic layer was separated, dried over Na2SO4 and the solvent removed under reduced pressure. The crude product was purified via silica gel column chromatography (0-50% EtOAc/isohexane) to give tert-butyl 6-fluoro-6-methyl-4-(1-methyl-4-nitro-1H-pyrazol-5-yl)-1,4-diazepane-1-carboxylate (70 mg, 70%) as a clear colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.03 (s, 1H), 3.80 (s, 3H), 3.73-3.32 (m, 6H), 3.26-3.03 (m, 2H), 1.50 (s, 9H), 1.32 (d, J=20.1 Hz, 3H).

Workup

  1. temperaturecooled in an ice water bath
  2. customquenched by dropwise addition of saturated aqueous NaHCO3 (40 mL)
  3. stirringThe resulting mixture was stirred for 10 min
  4. customThe organic layer was separated
  5. dry with materialdried over Na2SO4
  6. customthe solvent removed under reduced pressure
  7. customThe crude product was purified via silica gel column chromatography (0-50% EtOAc/isohexane)

Sources & evidence

ORD record
ord-ddbed45d3c834869937523fa3d79941e
Source dataset
uspto-grants-2013_12
Patent number
US08614206B2

Reaction notes

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