Acetic Acid → HCID 178421671, compound

HRID 474104Notes

Reaction equation

HRID 474104 reaction equation
[F-].[K+].[Br:3][C:4]1[N:9]=[C:8]([C:10]2([CH3:25])[CH2:12][N@@:11]2[S:13]([C:16]2[CH:21]=[CH:20][C:19]([N+:22]([O-:24])=[O:23])=[CH:18][CH:17]=2)(=[O:15])=[O:14])[C:7]([F:26])=[C:6]([Si](CC)(CC)CC)[CH:5]=1.CC(O)=O.C([O-])(O)=O.[Na+]>C1COCC1.CC(OC)(C)C.CN(C=O)C>[Br:3][C:4]1[N:9]=[C:8]([C:10]2([CH3:25])[CH2:12][N@@:11]2[S:13]([C:16]2[CH:17]=[CH:18][C:19]([N+:22]([O-:24])=[O:23])=[CH:20][CH:21]=2)(=[O:14])=[O:15])[C:7]([F:26])=[CH:6][CH:5]=1

Participants

8

Reactant 4

HCID 176Acetic AcidHCID 516892Sodium BicarbonateHCID 522689Potassium FluorideHCID 178477537HCID 178477537, compound

Product 1

HCID 178421671HCID 178421671, compoundYield 87.9%

Reagents, catalysts & solvents 3

HCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

Potassium fluoride (1.1 g, 18.85 mmol) was added to a solution of 6-bromo-3-fluoro-2-[(S)-2-methyl-1-(4-nitro-benzenesulfonyl)-aziridin-2-yl]-4-triethylsilanyl-pyridine (5 g, 9.43 mmol) and AcOH (1.13 g, 9.43 mmol) in 25 ml THF. DMF (35 ml) was added and the suspension was stirred for 1 h at rt. The reaction mixture was poured onto a mixture of sat. aq. NaHCO3 and TBME. The layers were separated and washed with brine and TBME. The combined organic layers were dried over MgSO4.H2O, filtered and evaporated to give a yellow oil which was crystallized from TBME/hexane to yield 3.45 g of the title compound as white crystals. HPLC: RtH13=2.612 min; ESIMS: 416, 418 [(M+H)+, 1Br]; 1H-NMR (400 MHz, CDCl3): 8.41 (d, 2H), 8.19 (d, 2H), 7.48 (dd, 1H), 7.35 (t, 1H), 3.14 (s, 1H), 3.03 (s, 1H), 2.04 (s, 3H); α[D]-35.7° (c=0.89, DCM).

Workup

  1. customThe layers were separated
  2. washwashed with brine and TBME
  3. dry with materialThe combined organic layers were dried over MgSO4.H2O
  4. filtrationfiltered
  5. customevaporated
  6. customto give a yellow oil which
  7. customwas crystallized from TBME/hexane

Sources & evidence

ORD record
ord-b83bbb621bb14ba7a6c3a356fd923c29
Source dataset
uspto-grants-2014_01
Patent number
US08637508B2

Reaction notes

Loading…