Oxygen → HCID 89180724, compound

HRID 1468720Notes

Reaction equation

HRID 1468720 reaction equation
[C:1]([O:5][C@@H:6]([C:12]1[C:22]([CH3:23])=[CH:21][C:15]2[N:16]=[C:17]([CH:19]=C)[S:18][C:14]=2[C:13]=1[O:24][S:25]([C:28]([F:31])([F:30])[F:29])(=[O:27])=[O:26])[C:7]([O:9][CH2:10][CH3:11])=[O:8])([CH3:4])([CH3:3])[CH3:2].C(Cl)Cl.[O:35]=O>CO>[C:1]([O:5][C@@H:6]([C:12]1[C:22]([CH3:23])=[CH:21][C:15]2[N:16]=[C:17]([CH:19]=[O:35])[S:18][C:14]=2[C:13]=1[O:24][S:25]([C:28]([F:29])([F:31])[F:30])(=[O:26])=[O:27])[C:7]([O:9][CH2:10][CH3:11])=[O:8])([CH3:2])([CH3:4])[CH3:3]

Participants

5

Reactant 3

HCID 977OxygenHCID 6344DichloromethaneHCID 89965892HCID 89965892, compound

Product 1

HCID 89180724HCID 89180724, compoundYield 97%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
0 °C

Procedure

A solution of 91A (170 mg, 0.353 mmol), DCM (5.0 mL), and MeOH (5.0 mL) was cooled to 78° C. and perfused with oxygen gas for 3 min. Then using an ozonator, a stream of O3 in oxygen gas was bubbled through the solution for 5 min. After this, the reaction was stirred for 10 min, then sparged with oxygen gas for 2 min to drive out unreacted ozone in solution. While the reaction was still at 78° C., dimethylsulfide (200 μL) was added and the reaction allowed to warm to 0° C. After 30 min, 10% w/v aq Na2S2O3 (5 mL) was added and the reaction was warmed to 23° C. and stirred for 10 min. The reaction was diluted with H2O (20 mL) and extracted with DCM (3×15 mL). Combined organic layers were dried (Na2SO4), filtered, and concentrated. More DCM was added and the reaction was concentrated once more to remove residual methanol, giving 91B (165 mg, 97% yield). 1H-NMR: 400 MHz, (CDCl3) δ: 10.04 (s, 1H), 8.00 (s, 1H), 5.60 (s, 1H), 4.22-4.00 (m, 2H), 2.51 (s, 3H), 1.16 (s, 9H), 1.14 (t, J=6.8 Hz, 3H). 19F-NMR: 376 MHz, (CDCl3) δ: −73.6.

Workup

  1. customa stream of O3 in oxygen gas was bubbled through the solution for 5 min
  2. customsparged with oxygen gas for 2 min
  3. customwas still at 78° C.
  4. additiondimethylsulfide (200 μL) was added
  5. waitAfter 30 min
  6. additionwas added
  7. temperaturethe reaction was warmed to 23° C.
  8. stirringstirred for 10 min
  9. additionThe reaction was diluted with H2O (20 mL)
  10. extractionextracted with DCM (3×15 mL)
  11. dry with materialCombined organic layers were dried (Na2SO4)
  12. filtrationfiltered
  13. concentrationconcentrated
  14. additionMore DCM was added
  15. concentrationthe reaction was concentrated once more
  16. customto remove residual methanol

Sources & evidence

ORD record
ord-ea46b11a92644d17b31741c60875e544
Source dataset
uspto-grants-2015_04
Patent number
US09006229B2

Reaction notes

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