tert-Butanol → Tert-butyl (3-methoxy-2-nitrophenyl)carbamate

HRID 2168946Notes

Reaction equation

HRID 2168946 reaction equation
[CH3:1][O:2][C:3]1[C:4]([N+:12]([O-:14])=[O:13])=[C:5]([CH:9]=[CH:10][CH:11]=1)C(O)=O.C([N:17]([CH2:20]C)CC)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:29])C=CC=CC=1.[CH3:39][C:40]([OH:43])([CH3:42])[CH3:41]>C1(C)C=CC=CC=1>[CH3:1][O:2][C:3]1[C:4]([N+:12]([O-:14])=[O:13])=[C:5]([NH:17][C:20](=[O:29])[O:43][C:40]([CH3:42])([CH3:41])[CH3:39])[CH:9]=[CH:10][CH:11]=1

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 8471Triethylamine2×HCID 786323-Methoxy-2-nitrobenzoic acidHCID 199401P,P-Diphenylphosphinic azide

Product 1

HCID 10587951Tert-butyl (3-methoxy-2-nitrophenyl)carbamate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
90 °C

Procedure

3-Methoxy-2-nitrobenzoic acid (10.25 g) was suspended in toluene (200 ml), and triethylamine (8.65 ml) and diphenylphosphoryl azide (13.4 ml) were added dropwise at room temperature. The mixture was stirred at 90° C. for 1.5 hr, triethylamine (29 ml) and 2-methylpropan-2-ol (15 ml) were added, and the mixture was further stirred at 90° C. for 2 hr. The reaction mixture was concentrated under reduced pressure, diluted with ethyl acetate, 0.5M hydrochloric acid (200 ml) was added, and the mixture was filtered through celite. The organic layer of the filtrate was collected, washed with saturated aqueous sodium hydrogen carbonate, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel chromatography, and a fraction eluted with ethyl acetate-hexane (5:95-1:1) was concentrated under reduced pressure to give the object product (10.18 g).

Workup

  1. stirringthe mixture was further stirred at 90° C. for 2 hr
  2. concentrationThe reaction mixture was concentrated under reduced pressure
  3. additiondiluted with ethyl acetate, 0.5M hydrochloric acid (200 ml)
  4. additionwas added
  5. filtrationthe mixture was filtered through celite
  6. customThe organic layer of the filtrate was collected
  7. washwashed with saturated aqueous sodium hydrogen carbonate
  8. dry with materialdried over anhydrous magnesium sulfate
  9. concentrationconcentrated under reduced pressure
  10. washa fraction eluted with ethyl acetate-hexane (5:95-1:1)
  11. concentrationwas concentrated under reduced pressure

Sources & evidence

ORD record
ord-e33127e66b3047538c6b55784a96c309
Source dataset
uspto-grants-2015_06
Patent number
US09045436B2

Reaction notes

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