tert-Butyl hydroperoxide → HCID 59294467, compound

HRID 1877392Notes

Reaction equation

HRID 1877392 reaction equation
[Cl:1][C:2]1[CH:26]=[CH:25][C:24]([Cl:27])=[CH:23][C:3]=1[O:4][C:5]1[C:10]([C:11]([N:13]2[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[CH2:16][CH2:15][CH2:14]2)=[O:12])=[CH:9][CH:8]=[CH:7][N:6]=1.C(=O)([O-])[OH:29].[Na+].C(OO)(C)(C)C>ClCCCl>[Cl:1][C:2]1[CH:26]=[CH:25][C:24]([Cl:27])=[CH:23][C:3]=1[O:4][C:5]1[C:10]([C:11]([N:13]2[C:22]3[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=3)[C:16](=[O:29])[CH2:15][CH2:14]2)=[O:12])=[CH:9][CH:8]=[CH:7][N:6]=1

Participants

5

Reactant 3

HCID 6410tert-Butyl hydroperoxideHCID 516892Sodium BicarbonateHCID 46195848HCID 46195848, compound

Product 1

HCID 59294467HCID 59294467, compoundYield 114.2%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

To a solution of [2-(2,5-dichloro-phenoxy)-pyridin-3-yl]-(3,4-dihydro-2H-quinolin-1-yl)-methanone (100 mg, 0.25 mmol, 1.0 equiv; Example 24) in anhydrous 1,2-dichloroethane (2 mL) was added sodium hydrogen carbonate (11 mg, 0.125 mmol, 0.5 equiv; [CAS RN 144-55-8]), tert-butyl hydroperoxide (189 mg, 227 μL, 1.25 mmol, 5.0 equiv, 5.5 M solution in decane; [CAS RN 75-91-2], TBHP) and dirhodium caprolactamate (1.7 mg, 0.0025 mmol, 0.01 equiv; [CAS RN 138984-26-6]; prepared according to M. P. Doyle, L. J. Westrum, W. N. E. Wolthuis, M. M. See, W. P. Boone, V. Bagheri, M. M. Pearson, J. Am. Chem. Soc. 1993, 115, 958-964). The reaction mixture was stirred at rt over night. Removal of the solvent mixture under reduced pressure and purification by silica column chromatography using a MPLC system (CombiFlash Companion, Isco Inc.) eluting with a gradient of heptane/ethyl acetate followed by preparative HPLC on reversed phase (Xterra® PrepMSC 18, 5 μm, 19×50 mm column equipped with a Gilson Liquid Handler 215 autosampler, two Rainin Dynamax® SD-300 pumps, a Sedex ELSD 75 lightscatter and a Dionex UVD 340S UV detector) eluting with a gradient of acetonitrile/water provided 59 mg (57%) of the title compound as a white solid. MS (ISP): 413.1 [M+H]+.

Workup

  1. customRemoval of the solvent mixture
  2. customunder reduced pressure and purification by silica column chromatography
  3. washeluting with a gradient of heptane/ethyl acetate
  4. customequipped with a Gilson Liquid Handler 215 autosampler, two Rainin Dynamax® SD-300 pumps
  5. washa Sedex ELSD 75 lightscatter and a Dionex UVD 340S UV detector) eluting with a gradient of acetonitrile/water

Sources & evidence

ORD record
ord-e15cd6a89b80486d813884e848addfd2
Source dataset
uspto-grants-2012_11
Patent number
US08309734B2

Reaction notes

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