Benzene → HCID 44192120, compound

HRID 1516959Notes

Reaction equation

HRID 1516959 reaction equation
[CH3:1][C:2]([C:13]1C=[CH:17][CH:16]=[CH:15][CH:14]=1)([O:4][CH2:5]CCCC(C)C=C)[CH3:3].CN([CH:22]=[O:23])C.O=O.[CH:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.[CH3:32]CCCCC>Cl[Pd]Cl.Cl[Cu].O>[CH2:5]([O:4][C:2]([CH3:1])([CH3:3])[CH2:13][CH2:14][CH2:15][CH:16]([CH3:17])[C:22](=[O:23])[CH3:32])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1

Participants

9

Reactant 5

HCID 241BenzeneHCID 977OxygenHCID 6228DimethylformamideHCID 8058Hexane2×HCID 69049399HCID 69049399, compound

Product 1

HCID 44192120HCID 44192120, compoundYield 56%

Reagents, catalysts & solvents 3

HCID 24290Palladium ChlorideCatalystHCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent

Procedure

Wacker-Tsuji oxidation of (1,1,5-trimethyl-hept-6-enyloxymethyl)-benzene in a PDMS thimble. A PDMS thimble containing PdCl2 (0.100 g, 0.564 mmol) and CuCl (0.564 g, 5.64 mmol) was placed in a 2-necked Schlenk flask with a stir bar. DMF (3.96 mL) and H2O (0.56 mL) were added to the inside of the PDMS thimble and the flask was capped with a rubber septum. A balloon filled with O2 was affixed to the septum and the reaction mixture was stirred at room temperature for 1 hour. The olefin starting material, 1,1,5-trimethyl-hept-6-enyloxymethyl)benzene (1.39 g, 5.64 mmol), was added to the reaction mixture and allowed to stir under an O2 atmosphere for 24 hours. The PDMS thimble was swelled with hexane (2×25 mL) for 12 hour with a stir bar on the exterior of the PDMS thimble. The hexane extracts were combined and the solvent was removed in vacuo. A 1H NMR spectrograph was recorded in CDCl3 to determine quantitative conversion of the starting material to the ketone product. 7-Benzyloxy-3,7-dimethyl-octan-2-one (0.828 g, 56% yield) was isolated as a clear liquid by column chromatography using hexanes/EtOAc (95/5). 1H NMR (300 MHz, CDCl3, δ): 7.24 (m, 5H), 4.39 (s, 2H), 2.51 (m, 1H), 2.11 (s, 3H), 1.66-1.34 (m, 6H), 1.23 (s, 6H), 1.07 (d, J=5.4 Hz, 3H). 13C NMR (75.48 MHz; CDCl3, δ): 212.6, 139.7, 128.1, 127.2, 126.9, 74.9, 63.5, 47.0, 40.5, 33.2, 27.9, 25.5, 21.5, 16.1. HRMS calcd for C7H13O 113.0966, found 113.0973. Calcd for C10H13O 149.0966, found 149.0973.

Workup

  1. customwas placed in a 2-necked Schlenk flask with a stir bar
  2. customthe flask was capped with a rubber septum
  3. stirringto stir under an O2 atmosphere for 24 hours
  4. customthe solvent was removed in vacuo

Sources & evidence

ORD record
ord-0bef943c27a44d6f9cf532abc3108c71
Source dataset
uspto-grants-2012_07
Patent number
US08227635B2

Reaction notes

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