Sodium hydride → 2-(1,1-Dioxo-1lambda6-[1,2]thiazinan-2-yl)-benzonitrile

HRID 1788146Notes

Reaction equation

HRID 1788146 reaction equation
[O:1]=[S:2]1(=[O:8])[CH2:7][CH2:6][CH2:5][CH2:4][NH:3]1.[H-].[Na+].F[C:12]1[CH:19]=[CH:18][CH:17]=[CH:16][C:13]=1[C:14]#[N:15]>CN(C)C=O.O>[O:1]=[S:2]1(=[O:8])[CH2:7][CH2:6][CH2:5][CH2:4][N:3]1[C:12]1[CH:19]=[CH:18][CH:17]=[CH:16][C:13]=1[C:14]#[N:15]

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 678552-FluorobenzonitrileHCID 3035081,4-Butanesultam

Product 1

HCID 235683982-(1,1-Dioxo-1lambda6-[1,2]thiazinan-2-yl)-benzonitrileYield 70.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Added to a solution of 1,1-dioxo[1,2]thiazinane (3.37 g, 25 mmol) in dimethylformamide (35 mL) was sodium hydride (0.675 g, 25 mmol, 95%) and the mixture stirred at room temperature for 15 min. 2-Fluorobenzonitrile (3.37 mL, 31.3 mmol) was added and the mixture stirred at 80° C. for 18 h. The mixture was cooled, diluted with water and extracted with ethyl acetate. The organic phase was washed with water and brine, then dried (Na2SO4) and concentrated. The residue was purified by flash chromatography (SiO2) eluting with 10%-100% ethyl acetate/hexane. The isolated solid was recrystallized from hot ethyl acetate/hexane (2:1) to give the title compound as white crystals (4.15 g, 70% yield). 1H-NMR (300 MHz, CDCl3) δ ppm: 7.70 (1H, dd, J=7.7,1.1 Hz), 7.64-7.53 (2H, m), 7.41 (1H, td, J=7.3, 1.6 Hz), 3.72 (2H, t, J=5.5 Hz), 3.32 (2H, t, J=6.0 Hz), 2.40-2.32 (2H, m), 2.05-1.97 (2H, m). LCMS [M+H]+ calcd for C11H12N2O2S: 237.06; found: 237.10.

Workup

  1. stirringthe mixture stirred at 80° C. for 18 h
  2. temperatureThe mixture was cooled
  3. extractionextracted with ethyl acetate
  4. washThe organic phase was washed with water and brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated
  7. customThe residue was purified by flash chromatography (SiO2)
  8. washeluting with 10%-100% ethyl acetate/hexane
  9. customThe isolated solid was recrystallized from hot ethyl acetate/hexane (2:1)

Sources & evidence

ORD record
ord-54748bdd89594df0aaed72131d2905b3
Source dataset
uspto-grants-2009_03
Patent number
US07511037B2

Reaction notes

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