Acetic Acid → HCID 90102892, compound

HRID 1051209Notes

Reaction equation

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

Participants

Conditions

Temperature: -70 °C

Procedure

A solution of (3-nitro-phenyl)-carbamic acid tert-butyl ester (1.20 g, 5.04 mmol) in THF (50 mL) was added ((trimethylsilyl)methyl)magnesium chloride (1.48 g, 10.1 mmol) at −70° C. under nitrogen gas. The solution was then stirred at −70° C. for one h. A solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (2.74 g, 12.1 mmol) in THF (30 mL) was added, the reaction was warmed to 0° C. and 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%v/v) and the aqueous phase was extracted three times with ethyl acetate. The combined organic layers were washed with brine and dried over magnesium sulfate. Filtration followed by concentration in vacuo gave a brown oil. Flash chromatography (80/20 hexanes/ethyl acetate) afforded (3-nitro-4-trimethylsilanylmethyl-phenyl)-carbamic acid tert-butyl ester (1.20 g, 73%) as a light oil.

Workup

temperaturethe reaction was warmed to 0° C.
stirringto stir at 0° C. for another hour
extractionthe aqueous phase was extracted three times with ethyl acetate
washThe combined organic layers were washed with brine
dry with materialdried over magnesium sulfate
filtrationFiltration
concentrationfollowed by concentration in vacuo
customgave a brown oil

Sources & evidence

ORD record: ord-64dfc5c41f0b4b819fad899a811ec854
Source dataset: uspto-grants-2016_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09388166B2

Reaction notes

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