Diisopropylethylamine → 2-Methylthio-5-nitro anisole

HRID 1691839Notes

Reaction equation

HRID 1691839 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][C:3]=1[O:11][CH3:12].CCN(C(C)C)C(C)C.[CH3:22][S-:23].[Na+]>C1COCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[CH3:12][O:11][C:3]1[CH:4]=[C:5]([N+:8]([O-:10])=[O:9])[CH:6]=[CH:7][C:2]=1[S:23][CH3:22]

Participants

7

Reactant 3

HCID 81531DiisopropylethylamineHCID 2301031-Iodo-2-methoxy-4-nitrobenzeneHCID 4378561Sodium methanethiolate

Product 1

HCID 6079362-Methylthio-5-nitro anisoleYield 68.4%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8028TetrahydrofuranSolvent

Procedure

2-Iodo-5-nitroanisole (5.58 g, 20.0 mmol), Pd2(dba)3 (0.025 eq, 457 mg), Xantphos (0.05 eq, 578 mg), Hunigs Base (1 eq, 3.48 ml) and sodium methanethiolate (1 eq, 1.40 g) were dissolved in THF. The mixture was heated to reflux overnight. Upon cooling the mixture was filtered through celite. The filtrate was concentrated in vacuo. The residue was purified by flash chromatography (4:1 Hexanes/Ethyl Acetate) to give 2-methoxy-1-methylsulfanyl-4-nitro-benzene (2.72 g, 68.3%) as a yellow crystalline solid.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux overnight
  3. temperatureUpon cooling the mixture
  4. filtrationwas filtered through celite
  5. concentrationThe filtrate was concentrated in vacuo
  6. customThe residue was purified by flash chromatography (4:1 Hexanes/Ethyl Acetate)

Sources & evidence

ORD record
ord-17817b9a6eb54073be343c4ddd317c4a
Source dataset
uspto-grants-2012_04
Patent number
US08153809B2

Reaction notes

Loading…