2-Nitrophenol → 2-[(2-Methylprop-2-en-1-yl)oxy]aniline

HRID 132577

Reaction equation

HRID 132577 reaction equation
Cl[CH2:2][C:3]([CH3:5])=[CH2:4].[N+:6]([C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[OH:15])([O-])=O.C(=O)([O-])[O-].[K+].[K+].S(S([O-])=O)([O-])=O.[Na+].[Na+]>S([O-])(O)(=O)=O.C([N+](CCCC)(CCCC)CCCC)CCC.CCO.C1COCC1.O.ClCCl.C1(C)C=CC=CC=1.C(#N)C>[CH3:5][C:3](=[CH2:4])[CH2:2][O:15][C:10]1[CH:11]=[CH:12][CH:13]=[CH:14][C:9]=1[NH2:6]

Participants

10

Reactant 4

HCID 69472-NitrophenolHCID 112413-Chloro-2-methyl-1-propeneHCID 11430Potassium Carbonate3×HCID 24489Sodium Dithionite2×

Product 1

HCID 136173332-[(2-Methylprop-2-en-1-yl)oxy]aniline

Reagents, catalysts & solvents 5

HCID 94433Tetrabutylammonium hydrogen sulfateCatalystHCID 1140TolueneSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolventHCID 18504229Ethanol tetrahydrofuran waterSolvent

Procedure

A mixture of 3-chloro-2-methyl-1-propene (5.43 g, 60 mmol), 2-nitrophenol (5.56 g, 40 mmol), potassium carbonate (11.05 g, 80 mmol), tetrabutylammonium hydrogen sulfate (0.271 g, 0.89 mmol) and acetonitrile (120 ml) was heated under reflux for 16 h. The mixture was portioned between toluene and aqueous potassium carbonate (5%), and the organic phase was dried and concentrated. The residue and sodium dithionite (13.9 g, 80 mmol) in EtOH-THF-H2O (2:1:1, 100 ml) was heated under reflux for 3 h and left over the weekend in the fridge. Then, additional sodium dithionite (7 g, 40 mmol) was added and the mixture was boiled for 2 h. The reaction mixture was portioned between dichloromethane and aqueous potassium carbonate (10%) and the organic layer was dried (Na2SO4). Concentrated of the solution gave the subtitle compound.

Workup

  1. temperaturewas heated
  2. temperatureunder reflux for 16 h
  3. customthe organic phase was dried
  4. concentrationconcentrated
  5. temperatureunder reflux for 3 h
  6. waitleft over the weekend in the fridge
  7. dry with materialthe organic layer was dried (Na2SO4)
  8. concentrationConcentrated of the solution

Sources & evidence

ORD record
ord-e7de82bca38447afb4fcc31b33f67a17
Source dataset
uspto-grants-2008_06
Patent number
US07388020B2

Linked notes

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