Hydrogen Peroxide → HCID 67328822, compound

HRID 1846167Notes

Reaction equation

HRID 1846167 reaction equation
Br[C:2]1[C:3]([O:25][CH3:26])=[CH:4][C:5]([N:22]([CH3:24])[CH3:23])=[N:6][C:7]=1[CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][O:18][CH2:19][O:20][CH3:21].[Li]CCCC.B([O-])([O-])[O-:33].OO.[OH-].[Na+]>C1COCC1.CCCCC.O>[CH3:23][N:22]([CH3:24])[C:5]1[N:6]=[C:7]([CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH2:16][CH2:17][O:18][CH2:19][O:20][CH3:21])[C:2]([OH:33])=[C:3]([O:25][CH3:26])[CH:4]=1

Participants

9

Reactant 5

HCID 784Hydrogen PeroxideHCID 14798Sodium HydroxideHCID 26574BorateHCID 67328691HCID 67328691, compoundHCID 178418339Butyllithium

Product 1

HCID 67328822HCID 67328822, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8003PentaneSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
23 °C

Procedure

To a stirred solution containing 114 mg (0.26 mmol) of 5-Bromo-4-methoxy-6-(10-(methoxymethoxy)decyl)-N,N-dimethylpyridin-2-amine in 5 mL of anhydrous THF were added 413 μL (0.66 mmol) of 1.6M n-BuLi in pentane. The reaction mixture was stirred at 23° C. for 10 minutes. Then, were added 89.0 μL (0.79 mmol) of trymethyl borate and the mixture was stirred at 23° C. for 30 minutes. Then, were added 684 μL (12.6 mmol) of 35% aq H2O2 followed by 684 μL of 1N NaOH. The reaction mixture was stirred at 23° C. for 2 h and then poured into 20 mL of water. The mixture was extracted with two 20-mL portions of ethyl acetate. The combined organic layer was washed with one 20-mL portion of brine, dried (MgSO4) and concentrated under diminished pressure. The residue was purified by chromatography on a silica gel column (2×10 cm). Elution with 1:1 hexanes-ethyl acetate afforded the expected product as a yellowish oil: yield 20 mg (21%); silica gel TLC Rf 0.1 (1:1 hexanes-ethyl acetate); 1H NMR (methanol) δ 1.29 (br s, 12H), 1.56 (br m, 4H), 2.66 (dd, 2H, J=7.6, 7.6 Hz), 3.00 (s, 6H), 3.29 (s, 3H), 3.48 (t, 2H, J=6.8 Hz), 3.90 (s, 3H), 4.56 (s, 2H) and 6.11 (s, 1H); 13C NMR (methanol-d4) δ 25.85, 28.06, 29.07, 29.11, 29.19, 29.24, 29.37, 30.10, 35.20, 38.17, 38.17, 53.94, 54.93, 67.46, 87.91, 95.98, 132.79, 143.67, 153.94 and 157.39; mass spectrum (APCI), m/z (M+H)+369.2760 (C20H37N2O4 requires 369.2753)

Workup

  1. stirringthe mixture was stirred at 23° C. for 30 minutes
  2. stirringThe reaction mixture was stirred at 23° C. for 2 h
  3. extractionThe mixture was extracted with two 20-mL portions of ethyl acetate
  4. washThe combined organic layer was washed with one 20-mL portion of brine
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated under diminished pressure
  7. customThe residue was purified by chromatography on a silica gel column (2×10 cm)
  8. washElution with 1:1 hexanes-ethyl acetate

Sources & evidence

ORD record
ord-165b3be3165e4d92a91b0ee4eabc9901
Source dataset
uspto-grants-2015_02
Patent number
US08952025B2

Reaction notes

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