Acetic Acid → HCID 86727438, compound

HRID 519070Notes

Reaction equation

HRID 519070 reaction equation
[CH3:1][CH:2]1[N:15]2[C:6]([CH2:7][O:8][C:9]3[C:14]2=[CH:13][C:12](B2OC(C)(C)C(C)(C)O2)=[C:11]([C:25]([F:28])([F:27])[F:26])[CH:10]=3)=[N:5][N:4]([CH2:29][O:30][CH2:31][CH2:32][Si:33]([CH3:36])([CH3:35])[CH3:34])[C:3]1=[O:37].CC(O)=[O:40].OO>O1CCOCC1>[OH:40][C:12]1[CH:13]=[C:14]2[C:9](=[CH:10][C:11]=1[C:25]([F:28])([F:26])[F:27])[O:8][CH2:7][C:6]1[N:15]2[CH:2]([CH3:1])[C:3](=[O:37])[N:4]([CH2:29][O:30][CH2:31][CH2:32][Si:33]([CH3:34])([CH3:35])[CH3:36])[N:5]=1

Participants

5

Reactant 3

HCID 176Acetic AcidHCID 784Hydrogen PeroxideHCID 86727437HCID 86727437, compound

Product 1

HCID 86727438HCID 86727438, compoundYield 50%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

To a solution of 4-methyl-6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-7-trifluoromethyl-2-(2-trimethylsilanyl-ethoxymethyl)-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one (0.500 g, 0.923 mmol) in dioxane (25 mL) was added AcOH (2.5 mL) and hydrogen peroxide (30%, 5 mL) and the reaction mixture was stirred at ambient temperature overnight. The solution was quenched by the addition of saturated Na2SO3 solution and the volatiles were evaporated in vacuo. The aqueous residue was extracted with EtOAc (3×20 mL) and the combined organic phases were dried over anhydrous Na2SO4, filtered and the filtrate was concentrated in vacuo. The residue was purified by column chromatography on silica gel (eluting with 5-20% EtOAc in petroleum ether) to give 6-hydroxy-4-methyl-7-trifluoromethyl-2-(2-trimethylsilanyl-ethoxymethyl)-2,10-dihydro-9-oxa-1,2,4a-triaza-phenanthren-3-one (0.200 g, 50%) as a white solid. 1H NMR (CDCl3, 400 MHz): δ 7.15 (s, 1H), 6.59 (s, 1H), 6.00 (s, 1H), 5.14 (m, 2H), 4.69 (m, 2H), 4.56 (m, 1H), 3.69 (t, J=8.4 Hz, 2H), 1.53 (d, J=6.4 Hz, 3H), 1.02 (m, 2H), 0.04 (s, 9H).

Workup

  1. customThe solution was quenched by the addition of saturated Na2SO3 solution
  2. customthe volatiles were evaporated in vacuo
  3. extractionThe aqueous residue was extracted with EtOAc (3×20 mL)
  4. dry with materialthe combined organic phases were dried over anhydrous Na2SO4
  5. filtrationfiltered
  6. concentrationthe filtrate was concentrated in vacuo
  7. customThe residue was purified by column chromatography on silica gel (eluting with 5-20% EtOAc in petroleum ether)

Sources & evidence

ORD record
ord-24af72b104294b97bd036db0fe65b4f6
Source dataset
uspto-grants-2015_08
Patent number
US09115151B2

Reaction notes

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