Cesium carbonate → [2-(4-Amino-3-nitro-phenyl)-ethyl]-carbamic acid benzyl ester

HRID 1777767

반응식

HRID 1777767 반응식
Br[C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1.[CH2:12]([O:19][C:20]([NH:22][CH2:23][CH2:24][B-](F)(F)F)=[O:21])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1.[K+].C1(P(C2CCCCC2)C2C=CC=CC=2C2C(OC)=CC=CC=2OC)CCCCC1.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.O.CC(=O)OCC.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH2:12]([O:19][C:20](=[O:21])[NH:22][CH2:23][CH2:24][C:2]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:9]([O-:11])=[O:10])[CH:3]=1)[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

참가 물질

8

반응물 4

HCID 10796Cesium carbonateHCID 701324-Bromo-2-nitroanilineHCID 112698722-Dicyclohexylphosphino-2',6'-dimethoxybiphenylHCID 49761741Potassium benzyl N-[2-(trifluoroboranuidyl)ethyl]carbamate

생성물 1

HCID 89726349[2-(4-Amino-3-nitro-phenyl)-ethyl]-carbamic acid benzyl ester수율 19.5%

시약·촉매·용매 3

HCID 167845palladium(II) acetate촉매HCID 8857Ethyl Acetate용매HCID 218864351,4-Dioxane--water (1/1)용매

실험 절차

A flask was charged with 4-bromo-2-nitroaniline (505 mg), potassium (2-(((benzyloxy)carbonyl)amino)ethyl)trifluoroborate (745 mg), Pd(OAc)2 (25.3 mg), 2-(dicyclohexylphosphino)-2′,6′-dimethoxybiphenyl (94.6 mg) and Cs2CO3 (2.2 g) in dioxane/water (20 mL/2 mL). The reaction mixture was refluxed for 92 h, cooled down, diluted with EA and washed with water and brine. The aq. layers were extracted with EA, the combined org. layers were dried (MgSO4), filtered off and evaporated to dryness. The residue was purified by CC (Biotage, SNAP 25 g cartridge, solvent A: Hept; solvent B: EA; gradient in % B: 10 for 3CV, 10 to 30 over 3CV, 30 for 4CV, 30 to 50 over 3CV, 50 for 5CV) to afford 143 mg of red oil. LC-MS (B): tR=0.85 min; [M]+: 316.07.

후처리

  1. temperatureThe reaction mixture was refluxed for 92 h
  2. temperaturecooled down
  3. washwashed with water and brine
  4. extractionThe aq. layers were extracted with EA
  5. dry with materiallayers were dried (MgSO4)
  6. filtrationfiltered off
  7. customevaporated to dryness
  8. customThe residue was purified by CC (Biotage, SNAP 25 g cartridge, solvent A: Hept; solvent B: EA; gradient in % B: 10 for 3CV, 10 to 30 over 3CV, 30 for 4CV, 30 to 50 over 3CV, 50 for 5CV)

출처 및 근거

ORD 기록
ord-be6342ebe1c8468a9fe891ac623a9f69
출처 데이터셋
uspto-grants-2016_02
특허 번호
US09266876B2

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