Sodium borohydride → HCID 67263796, compound

HRID 1688014Notes

Reaction equation

HRID 1688014 reaction equation
[S].[BH4-].[Na+].[CH2:4]([O:7][C:8]1[CH:9]=[C:10]([N:18]2[CH2:23][CH2:22][O:21][CH2:20][CH2:19]2)[CH:11]=[C:12]([F:17])[C:13]=1[N+:14]([O-])=O)[CH:5]=[CH2:6]>O1CCCC1>[CH2:4]([O:7][C:8]1[CH:9]=[C:10]([N:18]2[CH2:23][CH2:22][O:21][CH2:20][CH2:19]2)[CH:11]=[C:12]([F:17])[C:13]=1[NH2:14])[CH:5]=[CH2:6]

Participants

5

Reactant 3

HCID 4311764Sodium borohydrideHCID 5362487SulfurHCID 67264453HCID 67264453, compound

Product 1

HCID 67263796HCID 67263796, compoundYield 64.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
60 °C

Procedure

Sulfur (0.320 g, 9.98 mmol) was added to Sodium tetrahydroborate (0.126 g, 3.33 mmol) in Tetrahydrofuran (8 mL). After 5 min, a solution of 4-(3-Allyloxy-5-fluoro-4-nitro-phenyl)-morpholine (0.188 g, 0.666 mmol) in Tetrahydrofuran (6 mL) was added and the mixture was heated at 60° C. overnight. The mixture was cooled and diluted with 25 mL satd. sodium bicarbonate, then extracted 2×25 mL EtOAc. The organic extract was washed with water (10 mL) and brine (25 mL), then dried over sodium sulfate, and was concentrated in vacuo. The residue was partitioned between EtOAc (20 mL) and 1N HCl (20 mL); the resulting precipitate was filtered off. The filtrate was separated, the aq. washed 2×25 mL EtOAc, then neutralized with satd. sodium bicarbonate solution before being extracted with DCM (2×20 mL). The organic extract was dried over sodium sulfate and conc. in vacuo to afford 2-Allyloxy-6-fluoro-4-morpholin-4-yl-phenylamine (108 mg, 64%). LCMS: 253 (M+H); 1H-NMR (CDCl3): 6.30 (m, 2H), 6.06 (m, 1H), 5.42 (d, 1H, J=17 Hz), 5.29 (d, 1H, J=10.5 Hz), 4.55 (m, 2H), 3.80 (m, 4H), 3.49 (s, 2H), 3.00 (m, 4H); 19F-NMR (CDCl3): −133.

Workup

  1. temperatureThe mixture was cooled
  2. additiondiluted with 25 mL
  3. extractionsodium bicarbonate, then extracted 2×25 mL EtOAc
  4. extractionThe organic extract
  5. washwas washed with water (10 mL) and brine (25 mL)
  6. dry with materialdried over sodium sulfate
  7. concentrationwas concentrated in vacuo
  8. customThe residue was partitioned between EtOAc (20 mL) and 1N HCl (20 mL)
  9. filtrationthe resulting precipitate was filtered off
  10. customThe filtrate was separated
  11. washthe aq. washed 2×25 mL EtOAc
  12. extractionsodium bicarbonate solution before being extracted with DCM (2×20 mL)
  13. extractionThe organic extract
  14. dry with materialwas dried over sodium sulfate and conc. in vacuo

Sources & evidence

ORD record
ord-c4ee8a52aa7b48b29c23b53407341359
Source dataset
uspto-grants-2012_04
Patent number
US08148391B2

Reaction notes

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