Hydrochloric Acid → 3-Methoxy-4-(methylsulfanyl)phenol

HRID 724270Notes

Reaction equation

HRID 724270 reaction equation
[BH4-].[Na+].C([O:6][C:7]1[CH:12]=[CH:11][C:10]([S:13][CH3:14])=[C:9]([O:15][CH3:16])[CH:8]=1)C=C.Cl.O>C1COCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CCOC(C)=O>[CH3:16][O:15][C:9]1[CH:8]=[C:7]([OH:6])[CH:12]=[CH:11][C:10]=1[S:13][CH3:14]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 4311764Sodium borohydrideHCID 218771484-(Allyloxy)-2-methoxy-1-(methylsulfanyl)benzene

Product 1

HCID 218771303-Methoxy-4-(methylsulfanyl)phenolYield 56.5%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

Sodium borohydride (18.92 g, 0.5 mol) was added portionwise to a solution of 4-(allyloxy)-2-methoxy-1-(methylsulfanyl)benzene (26.0 g, 0.124 mol), and tetrakis(triphenylphosphine)palladium (0) (7.14 g, 6.18 mol) in THF (600 ml) at 5° C. The resultant solution was allowed to warm to RT and then heated to 45° C. for 14 h whilst protected under an atmosphere of nitrogen. After cooling in an ice-bath, the reaction mixture was acidified to pH5 with HCl (2M, 200 ml). Water (200 ml) and EtOAc (300 ml) were added, and the aqueous phase separated and extracted with EtOAc (2×200 ml). The combined organics were dried over MgSO4 and concentrated to a black solid (40 g) which was purified by flash column chromatography on silica gel eluting with EtOAc:pentane (1:9 to 3:7) to afford the title compound as a white solid (11.85 g, 0.07 mol).

Workup

  1. temperatureheated to 45° C. for 14 h
  2. temperatureAfter cooling in an ice-bath
  3. customthe aqueous phase separated
  4. extractionextracted with EtOAc (2×200 ml)
  5. dry with materialThe combined organics were dried over MgSO4
  6. concentrationconcentrated to a black solid (40 g) which
  7. customwas purified by flash column chromatography on silica gel eluting with EtOAc:pentane (1:9 to 3:7)

Sources & evidence

ORD record
ord-c32bfab2ad814d55a393ad7c4f4c56a7
Source dataset
uspto-grants-2006_11
Patent number
US07141586B2

Reaction notes

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