tert-Butanol → tert-Butyl (5-methoxy-2-nitrophenyl)carbamate

HRID 1259960Notes

Reaction equation

HRID 1259960 reaction equation
[CH3:1][O:2][C:3]1[CH:4]=[CH:5][C:6]([N+:12]([O-:14])=[O:13])=[C:7]([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[CH:4]=[CH:5][C:6]([N+:12]([O-:14])=[O:13])=[C:7]([NH:17][C:20](=[O:29])[O:43][C:40]([CH3:42])([CH3:41])[CH3:39])[CH:11]=1

Participants

6

Reactant 4

HCID 6386tert-ButanolHCID 8471Triethylamine2×HCID 199401P,P-Diphenylphosphinic azideHCID 3392095-Methoxy-2-nitrobenzoic acid

Product 1

HCID 10199249tert-Butyl (5-methoxy-2-nitrophenyl)carbamate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
95 °C

Procedure

5-Methoxy-2-nitrobenzoic acid (10.30 g) was suspended in toluene (200 ml), triethylamine (9 ml) and diphenylphosphoryl azide (14 ml) were added dropwise at room temperature, and the mixture was stirred at 95° C. for 1.5 hr. Triethylamine (29 ml) and 2-methylpropan-2-ol (15 ml) were added, and the mixture was further stirred at 95° C. for 3 hr. The reaction mixture was concentrated under reduced pressure, and 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 (13.28 g).

Workup

  1. stirringthe mixture was further stirred at 95° C. for 3 hr
  2. concentrationThe reaction mixture was concentrated under reduced pressure
  3. additiondiluted with ethyl acetate
  4. addition0.5M Hydrochloric acid (200 ml) was 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-186df48657cc458a8a2333f521431d30
Source dataset
uspto-grants-2013_06
Patent number
US08466282B2

Reaction notes

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