Water → 2,6-Dichloro-3-methoxyaniline

HRID 1038659Notes

Reaction equation

HRID 1038659 reaction equation
Cl.[Cl:2][C:3]1[C:8]([NH2:9])=[C:7]([Cl:10])[CH:6]=[CH:5][C:4]=1[OH:11].[OH-].[K+].S(OC)(O[CH3:18])(=O)=O.O>CC(C)=O>[Cl:2][C:3]1[C:4]([O:11][CH3:18])=[CH:5][CH:6]=[C:7]([Cl:10])[C:8]=1[NH2:9]

Participants

6

Reactant 4

HCID 962WaterHCID 6497Dimethyl SulfateHCID 14797Potassium HydroxideHCID 198981173-Amino-2,4-dichlorophenol hydrochloride

Product 1

HCID 205138882,6-Dichloro-3-methoxyaniline

Reagents, catalysts & solvents 1

HCID 180AcetoneSolvent

Procedure

To a solution of 2,4-dichloro-3-aminophenol hydrochloride (GLSynthesis, 7.70 g, 35.9 mmol, 1.0 eq.) in acetone is added powdered potassium hydroxide 85% (9.48 g, 143.6 mmol, 4.0 eq.) in small portions. Then, dimethyl sulfate (5.13 ml, 53.9 mmol, 1.5 eq.) is added at such a rate that the internal temperature does not rise above 30° C. After 1 h stirring at room temperature water (50 ml) is added and stirring is continued for another hour. The solvent is evaporated and the residue is distributed between ethyl acetate (150 ml) and water (100 ml). The organic layer is isolated, dried over Na2SO4 and evaporated to give a yellow oil. Kugelrohr distillation affords the desired product as a colorless oil: b.p. 150° C./0.3 mbar, HPLC: tR=5.61 min (purity: 90%, gradient A), 400 MHz 1H-NMR (CDCl3) δ: 3.87 (s, 3H, OMe), 4.49 (br s, 2H, NH2), 6.30 (d, 1H, Ar—H4), 7.11 (d, 1H, Ar—H5).

Workup

  1. customdoes not rise above 30° C
  2. additionis added
  3. waitis continued for another hour
  4. customThe solvent is evaporated
  5. customThe organic layer is isolated
  6. dry with materialdried over Na2SO4
  7. customevaporated
  8. customto give a yellow oil
  9. distillationKugelrohr distillation

Sources & evidence

ORD record
ord-b0f0b181d6d94258966beff57e8982d8
Source dataset
uspto-grants-2013_10
Patent number
US08552002B2

Reaction notes

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