Ethyl Acetate → 3,5-Dimethyl-4-(3'-iso-propyl-4'-methoxyphenylsulfanyl)anisole

HRID 2108638Notes

Reaction equation

HRID 2108638 reaction equation
CC(C)([O-])C.[K+].[CH3:7][O:8][C:9]1[CH:14]=[CH:13][C:12]([SH:15])=[CH:11][C:10]=1[CH:16]([CH3:18])[CH3:17].[CH3:19][C:20]1[CH:21]=[C:22]([O:28][CH3:29])[CH:23]=[C:24]([CH3:27])[C:25]=1I.C(OCC)(=O)C>C1(C)C=CC=CC=1.[I].[Cu]>[CH3:19][C:20]1[CH:21]=[C:22]([O:28][CH3:29])[CH:23]=[C:24]([CH3:27])[C:25]=1[S:15][C:12]1[CH:13]=[CH:14][C:9]([O:8][CH3:7])=[C:10]([CH:16]([CH3:18])[CH3:17])[CH:11]=1

Participants

7

Reactant 4

HCID 8857Ethyl AcetateHCID 147206012-Iodo-5-methoxy-1,3-dimethylbenzeneHCID 227269904-Methoxy-3-iso-propyl-thiophenolHCID 23665647Potassium tert-butoxide

Product 1

HCID 666428213,5-Dimethyl-4-(3'-iso-propyl-4'-methoxyphenylsulfanyl)anisoleYield 49%

Reagents, catalysts & solvents 2

HCID 178505378HCID 178505378, compoundCatalystHCID 1140TolueneSolvent

Procedure

Copper iodine (70 mg, 0.37 mmol), neocuprinine (80 mg, 0.37 mmol) and potassium t-butoxide (470 mg, 4.05 mmol) were added in this order to a solution of 4-methoxy-3-iso-propyl-thiophenol (U.S. Pat. No. 6,747,048 B2, 600 mg, 2.3 mmol) and 3,5-dimethyl-4-iodoanisole (678 mg, 3.72 mmol) in toluene (10 mL). After refluxing overnight, the cooled reaction mixture was poured into ethyl acetate (50 mL) and washed twice with 1 N HCl then brine. The organics were dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, hexane/ethyl acetate 100:0 to 40:1) to give 3,5-dimethyl-4-(3′-iso-propyl-4′-methoxyphenylsulfanyl)anisole (0.358 g, 49%); 1H NMR (200 MHz, DMSO-d6): δ 6.87-6.80(m, 4H), 6.56(m, 1H), 3.76(s, 3H), 3.71(s, 3H), 3.15(m, 1H), 2.34(s, 6H), 1.06(d, 6H, J=7 Hz); TLC conditions: Uniplate silica gel, 250 microns; Mobile phase=25% ethyl acetate in hexane; Rf=0.36

Workup

  1. temperatureAfter refluxing overnight
  2. customthe cooled reaction mixture
  3. washwashed twice with 1 N HCl
  4. dry with materialThe organics were dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated under reduced pressure
  7. customThe residue was purified by column chromatography (silica gel, hexane/ethyl acetate 100:0 to 40:1)

Sources & evidence

ORD record
ord-532d5fe85fa748738e4cae33833d6c1b
Source dataset
uspto-grants-2009_04
Patent number
US07514419B2

Reaction notes

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