Methane → Boc-aminonaphthol

HRID 1179135Notes

Reaction equation

HRID 1179135 reaction equation
Cl.N[C:3]1[C:12]2[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=2)[C:6]([OH:13])=[CH:5][CH:4]=1.C([N:16](CC)CC)C.[CH3:21][C:22]([O:25][C:26]([O:28]C(OC(C)(C)C)=O)=O)([CH3:24])[CH3:23].ClC(Cl)C.C>C1COCC1>[C:26]([C:4]1[C:5]([NH2:16])=[C:6]([OH:13])[C:7]2[C:12]([CH:3]=1)=[CH:11][CH:10]=[CH:9][CH:8]=2)([O:25][C:22]([CH3:24])([CH3:23])[CH3:21])=[O:28]

Participants

7

Reactant 5

HCID 297MethaneHCID 63651,1-DichloroethaneHCID 8471TriethylamineHCID 90495Di-tert-butyl dicarbonateHCID 27238584-Amino-1-naphthol hydrochloride

Product 1

HCID 69508617Boc-aminonaphtholYield 75.3%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

4-Aminonaphthalen-1-ol hydrochloride (50.0 g, 0.256 mol) was suspended in 500 mL THF under N2. Triethylamine (39.2 mL, 0.281 mol) was added dropwise from an addition funnel. The reaction was stirred for 30 min. Boc anhydride (55.79 g, 0.256 mol), dissolved in 60 mL THF was added dropwise. The reaction was heated to reflux for 5 h and then cooled first to room temperature first and then in a dry ice-acetone bath. The triethylamine HCl salt was filtered off and the precipitate was washed with small portions of THF. The filtrate was concentrated in vacuo leaving a thick brown oil. About 500 mL dichloroethane was added tom the oil and the solution was treated with a small amount of activated charcoal and then filtered through diatomaceous earth, using cold dichloroethane to wash the cake. The filtate was concentrated in vacuo providing the desired Boc-aminonaphthol product as a purple-browish solid (50 g).

Workup

  1. additionwas added dropwise
  2. temperatureThe reaction was heated
  3. temperatureto reflux for 5 h
  4. filtrationThe triethylamine HCl salt was filtered off
  5. washthe precipitate was washed with small portions of THF
  6. concentrationThe filtrate was concentrated in vacuo
  7. customleaving a thick brown oil
  8. filtrationfiltered through diatomaceous earth
  9. washto wash the cake
  10. concentrationThe filtate was concentrated in vacuo

Sources & evidence

ORD record
ord-73754e0b58214e29b5e9af19b6299159
Source dataset
uspto-grants-2007_10
Patent number
US07279475B2

Reaction notes

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