Hydrogen Peroxide → HCID 67464023, compound

HRID 2204073Notes

Reaction equation

HRID 2204073 reaction equation
[CH:1]1[N:9]2[C:4]([C:5]3([CH2:18][CH2:17][NH:16][CH2:15][CH2:14]3)[O:6][C:7]3[CH:13]=[CH:12][CH:11]=[CH:10][C:8]=32)=[CH:3][CH:2]=1.[OH:19][S:20]([OH:23])(=[O:22])=[O:21].[C:24](I)([F:27])([F:26])[F:25].OO>CS(C)=O>[S:20]([OH:23])([OH:22])(=[O:21])=[O:19].[F:25][C:24]([F:27])([F:26])[C:1]1[N:9]2[C:8]3[CH:10]=[CH:11][CH:12]=[CH:13][C:7]=3[O:6][C:5]3([CH2:18][CH2:17][NH:16][CH2:15][CH2:14]3)[C:4]2=[CH:3][CH:2]=1

Participants

6

Reactant 4

HCID 784Hydrogen PeroxideHCID 1118Sulfuric AcidHCID 16843TrifluoroiodomethaneHCID 58550727Spiro[benzo[b]pyrrolo[1,2-d][1,4]oxazine-4,4'-piperidine]

Product 1

HCID 67464023HCID 67464023, compoundYield 33%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

To spiro[piperidine-4,4′-pyrrolo[2,1-c][1,4]benzoxazine] (5.20 g, 21.6 mmol) in DMSO (104 mL) was added H2SO4 (1.27 mL, 23.8 mmol) (note: exothermic), ferrous sulfate heptahydrate (6.5 mL of 1.0 M, 6.5 mmol) followed by CF3I (4.24 g, 21.6 mmol) by slow bubbling through the solution and taking weight difference of cannister. The mixture cooled with a ice-water bath before H2O2 (2.45 mL of 30% w/v, 21.6 mmol) was added drop-wise over 10 min keeping temperature <23° C. The mixture was allowed to stir for 15 min before it was poured onto ice (250 g) producing a white precipitate. The slurry was stirred for 5 min and then the solid was collected via filtration. The off-white solid was taken up in acetonitrile (150 mL) and was heated at reflux of 1 h. The solvent was removed and the solid was recrystallized from EtOH (15 mL/g) and water (5 mL/g). The solid was collected and dried to give 1-(trifluoromethyl)spiro[benzo[b]pyrrolo[1,2-d][1,4]oxazine-4,4′-piperidine] sulfate (2.9 g, 33%). ESI-MS m/z calc. 308.1, found 309.1 (M+1)+; Retention time: 1.23 minutes (3 min run).

Workup

  1. customby slow bubbling through the solution
  2. additionwas added drop-wise over 10 min
  3. customtemperature <23° C
  4. additionwas poured onto ice (250 g)
  5. customproducing a white precipitate
  6. stirringThe slurry was stirred for 5 min
  7. filtrationthe solid was collected via filtration
  8. temperaturewas heated
  9. temperatureat reflux of 1 h
  10. customThe solvent was removed
  11. customthe solid was recrystallized from EtOH (15 mL/g) and water (5 mL/g)
  12. customThe solid was collected
  13. customdried

Sources & evidence

ORD record
ord-13cdf345ad054de1888cced5a3f6f4ad
Source dataset
uspto-grants-2016_06
Patent number
US09365588B2

Reaction notes

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