Acetic Acid → (2-Methoxy-5-nitro-4-trimethylsilanylmethyl-phenyl)-carbamic acid tert-butyl ester

HRID 1051221Notes

Reaction equation

HRID 1051221 reaction equation
[C:1]([O:5][C:6](=[O:19])[NH:7][C:8]1[CH:13]=[C:12]([N+:14]([O-:16])=[O:15])[CH:11]=[CH:10][C:9]=1[O:17][CH3:18])([CH3:4])([CH3:3])[CH3:2].[CH3:20][Si:21]([CH2:24][Mg]Cl)([CH3:23])[CH3:22].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.C(O)(=O)C>C1COCC1>[C:1]([O:5][C:6](=[O:19])[NH:7][C:8]1[CH:13]=[C:12]([N+:14]([O-:16])=[O:15])[C:11]([CH2:20][Si:21]([CH3:24])([CH3:23])[CH3:22])=[CH:10][C:9]=1[O:17][CH3:18])([CH3:4])([CH3:3])[CH3:2]

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 45790233Tert-butyl 2-methoxy-5-nitrophenylcarbamateHCID 178418680HCID 178418680, compound

Product 1

HCID 90102720(2-Methoxy-5-nitro-4-trimethylsilanylmethyl-phenyl)-carbamic acid tert-butyl esterYield 63.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-70 °C

Procedure

A solution of (2-methoxy-5-nitro-phenyl)-carbamic acid tert-butyl ester (1.80 g, 6.71 mmol) in THF (50 mL) was added ((trimethylsilyl)methyl)magnesium chloride (2.47 g, 16.8 mmol) at −70° C. under nitrogen gas. The solution was then stirred at −70° C. for one hour. A solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (3.05 g, 13.4 mmol) in THF (30 mL) was added, the reaction was warmed to 0° C. The reaction was allowed to stir at 0° C. for another hour. The reaction mixture is poured into an aqueous solution of acetic acid (50 mL, 5%). The aqueous phase was extracted three times with ethyl acetate and the combined organic layers were washed with brine and dried over magnesium sulfate. Filtration followed by concentration in vacuo gave brown oil. Flash chromatography (80/20 hexanes/ethyl acetate) afforded (2-methoxy-5-nitro-4-trimethylsilanylmethyl-phenyl)-carbamic acid tert-butyl ester (1.50 g, 63%) as a light oil.

Workup

  1. temperaturethe reaction was warmed to 0° C
  2. stirringto stir at 0° C. for another hour
  3. extractionThe aqueous phase was extracted three times with ethyl acetate
  4. washthe combined organic layers were washed with brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationFiltration
  7. concentrationfollowed by concentration in vacuo
  8. customgave brown oil

Sources & evidence

ORD record
ord-4eba50608b1e40a98a70d53d19779849
Source dataset
uspto-grants-2016_07
Patent number
US09388166B2

Reaction notes

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