Sulfuric acid magnesium salt (1:1) → HCID 23433661, compound

HRID 2121765Notes

Reaction equation

HRID 2121765 reaction equation
[C:1]([O:5][NH:6][C:7]([C:9]1[CH:10]=[C:11]([CH:13]=[CH:14][CH:15]=1)[NH2:12])=[O:8])([CH3:4])([CH3:3])[CH3:2].[O-]S([O-])(=O)=O.[Mg+2]>CC(C)=O.C(C1C=C(O)C(=CC=1)O)(C)(C)C.II>[C:1]([O:5][NH:6][C:7]([C:9]1[CH:10]=[C:11]2[C:13]([C:11]([CH3:13])=[CH:10][C:9]([CH3:15])([CH3:7])[NH:12]2)=[CH:14][CH:15]=1)=[O:8])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 2

HCID 24083Sulfuric acid magnesium salt (1:1)HCID 23433467HCID 23433467, compound2×

Product 1

HCID 23433661HCID 23433661, compoundYield 165.3%

Reagents, catalysts & solvents 3

HCID 807IodineCatalystHCID 73814-tert-ButylcatecholCatalystHCID 180AcetoneSolvent

Procedure

To an oven-dried 1 L r.b. flask containing 3-tert-butyloxycarbamoylaniline (17.4 g, 83.5 mmol), MgSO4 (50 g, 5 equivuiv), and 4-tert-butylcatechol (420 mg, 3 mol %) in 120 mL acetone (approx 0.75 M in the aniline) was added iodine (1.07 g, 5 mol %), and the mixture was heated to reflux for 8 h. The crude reaction mixture was then cooled to rt, filtered through a bed of Celite™ on a fritted-glass funnel, rinsing with ethyl acetate, dried (Na2SO4), and concentrated under reduced pressure. Purification by flash column chromatography (silica gel, hexanes/ethyl acetate, gradient elution) afforded 19.9 g (82%) of 7-tert-butyloxycarbamoyl-1,2-dihydro-2,2,4-trimethylquinoline as a white solid, which was further purified by recrystallization from acetonitrile to give white needles. Data for 7-tert-butyloxycarbamoyl-1,2-dihydro-2,2,4-trimethylquinoline: 1H NMR (400 MHz, CDCl3) 6.93 (d, J=8.3, 1H, 5-H), 6.81 (br s, 1H, HNBoc), 6.34 (m, 2H, 6,8-H), 5.21 (d, J=0.9, 1H, 3-H), 3.71 (br, s, 1H, NH), (d, J=1.0, 3H, 4-CH3), 1.50 [s, 9H, (CH3)3CO)], 1.24 [s, 6H, 2-(CH3)2].

Workup

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 8 h
  3. customThe crude reaction mixture
  4. filtrationfiltered through a bed of Celite™ on a fritted-glass funnel
  5. washrinsing with ethyl acetate
  6. dry with materialdried (Na2SO4)
  7. concentrationconcentrated under reduced pressure
  8. customPurification
  9. washby flash column chromatography (silica gel, hexanes/ethyl acetate, gradient elution)

Sources & evidence

ORD record
ord-6e0d1fc4a9f74df1a1ac4521a68fb315
Source dataset
uspto-grants-2004_02
Patent number
US06696459B1

Reaction notes

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