Hydrochloric Acid → HCID 57955652, compound

HRID 1880906Notes

Reaction equation

HRID 1880906 reaction equation
[Cl:1][C:2]1[N:7]=[C:6]([N:8]([CH:20]2[CH2:24][CH2:23][C@@H:22]([CH3:25])[CH2:21]2)[CH2:9][C:10]([F:19])([F:18])[C:11](=[O:17])C(OCC)=O)[C:5]([N+:26]([O-])=O)=[CH:4][N:3]=1.Cl.CCOC(C)=O.CCOCC>CC(O)=O.[Fe]>[Cl:1][C:2]1[N:3]=[CH:4][C:5]2[NH:26][C:11](=[O:17])[C:10]([F:19])([F:18])[CH2:9][N:8]([CH:20]3[CH2:24][CH2:23][C@@H:22]([CH3:25])[CH2:21]3)[C:6]=2[N:7]=1

Participants

7

Conditions

Temperature
60 °C

Procedure

Compound ethyl 4-((2-chloro-5-nitropyrimidin-4-yl)((3R)-3-methylcyclopentyl)amino)-3,3-difluoro-2-oxobutanoate was dissolved in AcOH and then cooled in an ice bath (sometimes this crystallizes out upon cooling). Iron powder (2 equivalents) was added followed by the slow addition of HCl (15 mL, conc.). After 10 minutes the reaction was transferred to a heat bath and left to stir at 60° C. for 5 hours. The reaction was then cooled, the stir bar and unreacted iron removed with a magnet (or by filtration through paper), and the solvent volume reduced by about 75% on a rotovap. The mixture was then diluted with ice water (150 mL) and EtOAc (1500 mL), the layers separated, the aqueous layer washed with EtOAc (2×150 mL), the organic extracts combined, washed with sat. NaHCO3 (100 mL), brine (100 mL), dried over MgSO4, filtered and concentrated to yield a brown syrup. Trituration with EtOAc (15 mL) and ether (100 mL) to coax out a tannish solid. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.91-2.29 (m, 10 H) 3.80-4.20 (m, 2 H) 4.81-5.07 (m, 1 H) 8.12 (s, 1 H) 11.07 (br. s., 1 H). m/z 317.

Workup

  1. temperaturecooled in an ice bath (sometimes
  2. customthis crystallizes out
  3. temperatureupon cooling)
  4. waitleft
  5. temperatureThe reaction was then cooled
  6. customthe stir bar and unreacted iron removed with a magnet (or by filtration through paper)
  7. additionThe mixture was then diluted with ice water (150 mL) and EtOAc (1500 mL)
  8. customthe layers separated
  9. washthe aqueous layer washed with EtOAc (2×150 mL)
  10. washwashed with sat. NaHCO3 (100 mL), brine (100 mL)
  11. dry with materialdried over MgSO4
  12. filtrationfiltered
  13. concentrationconcentrated
  14. customto yield a brown syrup

Sources & evidence

ORD record
ord-3ba2302627d243cdb1c69bd2852d21da
Source dataset
uspto-grants-2012_11
Patent number
US08318727B2

Reaction notes

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