Hydrogen Peroxide → HCID 86692736, compound

HRID 1184413Notes

Reaction equation

HRID 1184413 reaction equation
C([C@@H]1COC(=O)[N:9]1[C:14]([C@@H:16]1[CH2:21][CH2:20][C:19](=[O:22])[CH2:18][C@H:17]1[C:23]1[CH:28]=[CH:27][C:26]([Br:29])=[CH:25][CH:24]=1)=[O:15])C1C=CC=CC=1.CC(C)(CO)C[OH:33].C[C:38]1[CH:39]=[CH:40][C:41](S(O)(=O)=O)=[CH:42][CH:43]=1.OO.[Li+].[OH-].[C:52]1(C)[CH:57]=[CH:56][CH:55]=[CH:54][CH:53]=1>>[Br:29][C:26]1[CH:27]=[CH:28][C:23]([C@@H:17]2[CH2:18][C:19](=[O:22])[CH2:20][CH2:21][C@H:16]2[C:14]([O-:15])=[O:33])=[CH:24][CH:25]=1.[CH:52]1([NH2+:9][CH:38]2[CH2:39][CH2:40][CH2:41][CH2:42][CH2:43]2)[CH2:57][CH2:56][CH2:55][CH2:54][CH2:53]1

Participants

7

Reactant 6

HCID 784Hydrogen PeroxideHCID 1140TolueneHCID 3939Lithium HydroxideHCID 6101p-Toluenesulfonic acidHCID 31344Neopentyl glycolHCID 72546733HCID 72546733, compound

Product 1

HCID 86692736HCID 86692736, compound

Procedure

The product of Step B (10 g, 21.91 mmol) was dissolved in toluene (50 mL) and 2,2-dimethylpropane-1,3-diol (2.51 g, 24.11 mmol) and catalytic TsOH were added. The solution was refluxed for 3 h with a Dean-Stark trap in place, then cooled to rt, concentrated and flushed with THF. The product was dissolved in THF (70 mL), and cooled in an ice/acetone bath to 0° C. Hydrogen peroxide (5.76 mL, 35%, 65.7 mmol), followed by LiOH (1.05 g, 43.8 mmol in 8 mL water) were added and the mixture was allowed to warm and age at rt. The reaction mixture was acidified and heated to 60° C. for 1 h, then re-cooled to rt, and extracted with MTBE. The organic layer was collected, dried (Na2SO4), filtered and concentrated. The crude product was re-dissolved in MTBE and N-cyclohexylcyclohexanamine was added. The resulting slurry was aged for 1 h and filtered. The wet cake was washed with MTBE and the solid was dried under a vacuum/N2 sweep to afford the title compound.

Workup

  1. temperatureThe solution was refluxed for 3 h with a Dean-Stark trap in place
  2. concentrationconcentrated
  3. customflushed with THF
  4. dissolutionThe product was dissolved in THF (70 mL)
  5. temperaturecooled in an ice/acetone bath to 0° C
  6. additionwere added
  7. temperatureto warm
  8. customat rt
  9. temperatureheated to 60° C. for 1 h
  10. temperaturere-cooled to rt
  11. extractionextracted with MTBE
  12. customThe organic layer was collected
  13. dry with materialdried (Na2SO4)
  14. filtrationfiltered
  15. concentrationconcentrated
  16. dissolutionThe crude product was re-dissolved in MTBE
  17. additionN-cyclohexylcyclohexanamine was added
  18. filtrationfiltered
  19. washThe wet cake was washed with MTBE
  20. dry with materialthe solid was dried under a vacuum/N2 sweep

Sources & evidence

ORD record
ord-c5aad770e13940d0b2c063f27508f9d8
Source dataset
uspto-grants-2014_03
Patent number
US08669252B2

Reaction notes

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