tert-Butanol → (2-Bromo-3-methyl-5-nitro-phenyl)-carbamic acid tert-butyl ester

HRID 723254Notes

Reaction equation

C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=O)C=CC=CC=1.[Br:18][C:19]1[C:27](C)=[CH:26][C:25]([N+:29]([O-:31])=[O:30])=[CH:24][C:20]=1[C:21](O)=O.C([N:34]([CH2:37]C)CC)C.CC[O:41]C(C)=O.[C:45]([OH:49])([CH3:48])([CH3:47])[CH3:46]>>[C:45]([O:49][C:37](=[O:41])[NH:34][C:27]1[CH:26]=[C:25]([N+:29]([O-:31])=[O:30])[CH:24]=[C:20]([CH3:21])[C:19]=1[Br:18])([CH3:48])([CH3:47])[CH3:46]

Participants

Reactant 5

HCID 6386tert-Butanol

HCID 8471Triethylamine

HCID 8857Ethyl Acetate

HCID 199401P,P-Diphenylphosphinic azide

HCID 214691872-Bromo-3-methyl-5-nitrobenzoic acid

Product 1

HCID 57532227(2-Bromo-3-methyl-5-nitro-phenyl)-carbamic acid tert-butyl ester

Conditions

Temperature: 80 °C

Procedure

Diphenylphosphorylazide (453 μL, 2.1 mmol) was added to a stirred solution of 2-bromo-3-methyl-5-nitro-benzoic acid ((Example 295: step e) 520 mg, 2 mmol) and triethylamine (1.4 mL, 2.1 mmol) in tert-butanol (25 mL) at rt. After 15 minutes, the reaction was heated to 80° C. for 16 h. EtOAc (100 mL) was added and the solution was extracted with solutions of citric acid (3×30 mL), NaHCO3, (2×30 mL) and brine (50 mL). Purification by column chromatography yielded the title compound as a white solid. 1H NMR (CDCl3) δ 8.93 (d, 1H, J=2.6 Hz), 7.77 (app dd, 1H, J=0.7, 2.8 Hz), 7.26 (br s, 1H), 2.51 (s, 3H), 1.55 (s, 9H).

Workup

extractionthe solution was extracted with solutions of citric acid (3×30 mL), NaHCO3, (2×30 mL) and brine (50 mL)
customPurification by column chromatography

Sources & evidence

ORD record: ord-d7c86e9c01cd4c6ca7a0d8541f2d9fdc
Source dataset: uspto-grants-2006_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07138530B2

Reaction notes

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