Sulfoxonium, trimethyl-, iodide (1:1) → (5-Cyclopropyl-2-nitro-4-trifluoromethyl-phenyl)-carbamic acid tert-butyl ester

HRID 498173

반응식

HRID 498173 반응식
[C:1]([O:5][C:6](=[O:23])[NH:7][C:8]1[CH:13]=[C:12]([CH:14]=[CH2:15])[C:11]([C:16]([F:19])([F:18])[F:17])=[CH:10][C:9]=1[N+:20]([O-:22])=[O:21])([CH3:4])([CH3:3])[CH3:2].[I-].[CH3:25][S+](C)(C)=O>[Cl-].C([N+](CC)(CC)CC)C1C=CC=CC=1.[OH-].[Na+].C(Cl)Cl.CCOC(C)=O>[C:1]([O:5][C:6](=[O:23])[NH:7][C:8]1[CH:13]=[C:12]([CH:14]2[CH2:25][CH2:15]2)[C:11]([C:16]([F:18])([F:19])[F:17])=[CH:10][C:9]=1[N+:20]([O-:22])=[O:21])([CH3:2])([CH3:3])[CH3:4]

참가 물질

7

반응물 2

HCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 69486631(2-Nitro-4-trifluoromethyl-5-vinyl-phenyl)-carbamic acid tert-butyl ester

생성물 1

HCID 69489771(5-Cyclopropyl-2-nitro-4-trifluoromethyl-phenyl)-carbamic acid tert-butyl ester

시약·촉매·용매 4

HCID 66133Benzyl triethylammonium chloride촉매HCID 6344Dichloromethane용매HCID 8857Ethyl Acetate용매HCID 14798Sodium Hydroxide용매

반응 조건

온도
23 °C

실험 절차

A mixture of (2-nitro-4-trifluoromethyl-5-vinyl-phenyl)-carbamic acid tert-butyl ester (Example A27) (1.66 g, 5 mmol), trimethylsulfoxonium iodide (2.75 g, 12.5 mmol) and benzyltriethylammonium chloride (200 mg, 0.878 mmol) in NaOH 50% (15 ml) and DCM (25 ml) was stirred at 23° C. for 2 days. The mixture was diluted with EtOAc and washed with 1N HCl, water and brine, dried over MgSO4. Removal of the solvent invacuum left a dark brown oil, which was purified by silica gel column chromatography to give the title compound a yellow solid (659 mg). Residual starting material was removed as follows: To a solution of the obtained material (659 mg, 1.9 mmol) in EtOAc (11.5 ml) and MeCN (11.5 ml), a solution of RuCl3 (30 mg, 0.133 mmol) and NaIO4 (610 mg, 2.85 mmol) in H2O (3.8 ml) was added under vigurous stirring at 0° C. The mixture was being stirred for a further 3 min and then quenched with a sat. sol. of Na2S2O3 (19 ml). The mixture was diluted with EtOAc, the aqueous layer was separated, extracted once with EtOAc. The combined EtOAc layers were washed with brine, dried over MgSO4 and charcoal, filtered over dicalite, evaporated and purified by column chromatography on silica gel (heptane/ethyl acetate 9:1) to yield a yellow solid (630 g, 36%).

후처리

  1. washwashed with 1N HCl, water and brine
  2. dry with materialdried over MgSO4
  3. customRemoval of the solvent invacuum
  4. waitleft a dark brown oil, which
  5. customwas purified by silica gel column chromatography

출처 및 근거

ORD 기록
ord-2f81d61ccc8742b78ca92c244d047f1f
출처 데이터셋
uspto-grants-2005_09
특허 번호
US06949542B2

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