4-Nitrophenol → Chloromethyl 4-nitrophenyl carbonate

HRID 554033Notes

Reaction equation

HRID 554033 reaction equation
[CH:1]1[C:6]([N+:7]([O-:9])=[O:8])=[CH:5][CH:4]=[C:3]([OH:10])[CH:2]=1.Cl[C:12]([O:14][CH2:15][Cl:16])=[O:13].C(N(CC)CC)C>O1CCCC1>[C:12](=[O:13])([O:10][C:3]1[CH:4]=[CH:5][C:6]([N+:7]([O-:9])=[O:8])=[CH:1][CH:2]=1)[O:14][CH2:15][Cl:16]

Participants

5

Reactant 3

HCID 9804-NitrophenolHCID 8471TriethylamineHCID 62754Chloromethyl chloroformate

Product 1

HCID 2777826Chloromethyl 4-nitrophenyl carbonateYield 95%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

p-Nitrophenol (100 g, 0.72 moles) was dissolved in anhydrous tetrahydrofuran (3 L) and stirred vigorously. To this solution was added chloromethyl chloroformate (70 mL, 0.79 moles) at room temperature followed by triethylamine (110 mL). After stirring for 1 hour, the reaction mixture was filtered and the filtrate was concentrated and then diluted with ethyl acetate (1 L). The organic solution was washed with 10% potassium carbonate (3×500 mL) and 1N HCl (2×300 mL), brine (2×300 mL) and dried over anhydrous sodium sulfate. Removal of the solvent gave 157 g (95%) of the title compound (52) as a solid. The compound was unstable to LC-MS. 1H NMR (CDCl3, 400 MHz): 5.86 (s, 2H), 7.44 (d, J=9 Hz, 2H), 8.33 (d, J=9 Hz, 2H).

Workup

  1. stirringAfter stirring for 1 hour
  2. filtrationthe reaction mixture was filtered
  3. concentrationthe filtrate was concentrated
  4. additiondiluted with ethyl acetate (1 L)
  5. washThe organic solution was washed with 10% potassium carbonate (3×500 mL) and 1N HCl (2×300 mL), brine (2×300 mL)
  6. dry with materialdried over anhydrous sodium sulfate
  7. customRemoval of the solvent

Sources & evidence

ORD record
ord-038667e5666c4483a31d7ccc48a44426
Source dataset
uspto-grants-2011_11
Patent number
US08048917B2

Reaction notes

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