tert-Butanol → Tert-butyl 5-fluoro-2-nitrophenylcarbamate

HRID 252825ノート

反応式

HRID 252825 の反応式
[F:1][C:2]1[CH:3]=[CH:4][C:5]([N+:11]([O-:13])=[O:12])=[C:6]([CH:10]=1)C(O)=O.C([N:17]([CH:20](C)C)CC)(C)C.C1(P(N=[N+]=[N-])(C2C=CC=CC=2)=[O:30])C=CC=CC=1.[C:40]([OH:44])([CH3:43])([CH3:42])[CH3:41]>>[F:1][C:2]1[CH:3]=[CH:4][C:5]([N+:11]([O-:13])=[O:12])=[C:6]([NH:17][C:20](=[O:30])[O:44][C:40]([CH3:43])([CH3:42])[CH3:41])[CH:10]=1

参加物

5

反応物 4

HCID 6386tert-ButanolHCID 81531DiisopropylethylamineHCID 199401P,P-Diphenylphosphinic azideHCID 27374205-Fluoro-2-nitrobenzoic acid

生成物 1

HCID 44203079Tert-butyl 5-fluoro-2-nitrophenylcarbamate収率 87%

反応条件

温度
90 °C

実験手順

A flame-dried pressure vessel was charged with 5-fluoro-2-nitrobenzoic acid 118 (5.00 g, 27.0 mmol) and dry t-butyl alcohol (50 mL). To this solution were successively added N,N-di-isopropyl-N-ethylamine (5 mL) and diphenylphosphorylazide (6.42 mL, 29.7 mmol). The vessel was closed with teflon cap and the mixture was heated at 90° C. for 2 h. It was then allowed to cool to r.t. over 16 h. The solvent was removed in vacuo and the residue was partitioned between EtOAc and H2O. The aqueous layer was extracted with fresh EtOAc and the combined organic layers were washed with HCl 1N, sat. NaHCO3, brine, dried over MgSO4, filtered and concentrated. The resulting yellow oil was purified by flash chromatography on silica gel using EtOAc/hexanes (10:90) as an eluent, affording the title compound 119 (6.03 g, 87% yield) as light yellow crystals. LRMS: (m/z): 279.3 (M+Na+).

後処理

  1. customcap
  2. temperatureto cool to r.t. over 16 h
  3. customThe solvent was removed in vacuo
  4. customthe residue was partitioned between EtOAc and H2O
  5. extractionThe aqueous layer was extracted with fresh EtOAc
  6. washthe combined organic layers were washed with HCl 1N, sat. NaHCO3, brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe resulting yellow oil was purified by flash chromatography on silica gel

出典と根拠

ORDレコード
ord-506ba34a956646debc43d6db720cad50
出典データセット
uspto-grants-2011_01
特許番号
US07868205B2

反応ノート

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