Hydrochloric Acid → 3-Chloro-2-methoxyphenol

HRID 2408880Notes

Reaction equation

HRID 2408880 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4](Cl)[C:3]=1[O:9][CH3:10].[OH-:11].[K+].CC(C1C=C(C(C)C)C(C2C(P(C(C)(C)C)C(C)(C)C)=CC=CC=2)=C(C(C)C)C=1)C.Cl>O1CCOCC1.O.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]>[Cl:1][C:2]1[C:3]([O:9][CH3:10])=[C:4]([OH:11])[CH:5]=[CH:6][CH:7]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 14797Potassium HydroxideHCID 161272,6-DichloroanisoleHCID 11618717Di-tert-butyl(2',4',6'-tris(propan-2-yl)-(1,1'-biphenyl)-2-yl)phosphane

Product 1

HCID 1570043-Chloro-2-methoxyphenolYield 62%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
100 °C

Procedure

A reaction mixture of 1,3-dichloro-2-methoxybenzene (885 mg, 5 mmol), potassium hydroxide (280 mg, 5 mmol), tris(dibenzylideneacetone)dipalladium (115 mg, 0.125 mmol) and tert-butyl X-Phos (159 mg, 0.375 mmol) in dioxane/water (1:1, 5 mL) was stirred at 100° C. for 2 hours. The reaction mixture was mixed with aqueous hydrochloride solution (1 N). The organic components were extracted with EtOAc. The combined EtOAc layers were washed with brine, and then concentrated. The residue was purified by chromatography. Elution with 10% EtOAc in hexane gave 3-chloro-2-methoxyphenol (22-1, 489 mg, 62% yield) as yellow oil. 1H NMR (400 MHz, CDCl3) δ 6.98-6.84 (m, 3H), 5.73 (br s, 1H), 3.93 (s, 3H).

Workup

  1. extractionThe organic components were extracted with EtOAc
  2. washThe combined EtOAc layers were washed with brine
  3. concentrationconcentrated
  4. customThe residue was purified by chromatography
  5. washElution with 10% EtOAc in hexane

Sources & evidence

ORD record
ord-a2977d6aac52496693eb85aca0f7dc6e
Source dataset
uspto-grants-2014_08
Patent number
US08815875B2

Reaction notes

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