Aniline → 5-Methoxy-2-methylbenzene-1,3-diol

HRID 2272816Notes

Reaction equation

HRID 2272816 reaction equation
C(OC1C=CC(C(OC)=O)=CC=1CC=C)(=O)C.C(OC1C=CC(C(OC)=O)=CC=1CC=C(C)C)(=O)C.COCOCOC.COCCl.CCN(C(C)C)C(C)C.NC1C=CC=CC=1.[H][H].[CH3:66][O:67][C:68]1[CH:69]=[C:70]([O:79]COC)[C:71]([CH3:78])=[C:72]([O:74]COC)[CH:73]=1>CN(C)C=O.O1CCCC1.[Pd]>[CH3:66][O:67][C:68]1[CH:69]=[C:70]([OH:79])[C:71]([CH3:78])=[C:72]([OH:74])[CH:73]=1

Participants

12

Reactant 8

HCID 6115AnilineHCID 7864Chloromethyl Methyl EtherHCID 12362Bis(methoxymethyl)etherHCID 81531DiisopropylethylamineHCID 251387855-Methoxy-1,3-bis(methoxymethoxy)-2-methylbenzeneHCID 57940298Methyl 4-acetoxy-3-(3-methylbut-2-enyl)benzoateHCID 67094163Methyl 4-acetoxy-3-allylbenzoateHCID 178418361HCID 178418361, compound

Product 1

HCID 2387695-Methoxy-2-methylbenzene-1,3-diol

Reagents, catalysts & solvents 3

HCID 23938PalladiumCatalystHCID 6228DimethylformamideSolventHCID 8028TetrahydrofuranSolvent

Procedure

The preparation of intermediate 6 is described and illustrated below. The coumarin phenol 7 was converted to the methoxymethyl ether using methoxymethyl chloride and Hunig's base in Dimethylformamide. The free aniline, liberated through hydrogenolysis with 10% Pd/C and hydrogen in tetrahydrofuran from 7, was coupled with acid chloride 9 to give benzamide 10. Subsequent cleavage of the methoxymethyl ether with 4N hydrochloride in dioxane provided phenol 6 in high yield.

Sources & evidence

ORD record
ord-d3ff04d5260d4fc8983da3b14a5af1ea
Source dataset
uspto-grants-2015_09
Patent number
US09120774B2

Reaction notes

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