Cesium carbonate → tert-butyl 4-(2-amino-3-nitrophenyl)-5,6-dihydropyridine-1(2H)-carboxylate

HRID 406498

반응식

HRID 406498 반응식
Cl[C:2]1[CH:8]=[CH:7][CH:6]=[C:5]([N+:9]([O-:11])=[O:10])[C:3]=1[NH2:4].CC1(C)C(C)(C)OB([C:20]2[CH2:25][CH2:24][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:22][CH:21]=2)O1.C(=O)([O-])[O-].[Cs+].[Cs+].F[B-](F)(F)F.C(P(C(C)(C)C)C(C)(C)C)(C)(C)C>O1CCOCC1.O.CCCCCCC>[NH2:4][C:3]1[C:5]([N+:9]([O-:11])=[O:10])=[CH:6][CH:7]=[CH:8][C:2]=1[C:20]1[CH2:25][CH2:24][N:23]([C:26]([O:28][C:29]([CH3:32])([CH3:31])[CH3:30])=[O:27])[CH2:22][CH:21]=1

참가 물질

8

반응물 4

HCID 10796Cesium carbonateHCID 698552-Chloro-6-nitroanilineHCID 4642098Tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1,2,3,6-tetrahydropyridine-1-carboxylateHCID 44558591Tri-t-butylphosphine fluoroborate

생성물 1

HCID 68974308tert-butyl 4-(2-amino-3-nitrophenyl)-5,6-dihydropyridine-1(2H)-carboxylate수율 56.3%

시약·촉매·용매 3

HCID 962Water용매HCID 8900Heptane용매HCID 312751,4-Dioxane용매

실험 절차

A solution containing 2-chloro-6-nitroaniline (0.83 g, 4.8 mmol), tert-butyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5,6-dihydropyridine-1(2H)-carboxylate (2.97 g, 9.6 mmol), and cesium carbonate (3.13 g, 9.6 mmol) in dioxane (32 mL) and water (6 mL) was degassed with nitrogen and tris(dibenzylideneacetone)palladium(0) (0.22 g, 0.24 mmol) was added followed by the addition of tri-t-butylphosphine tetrafluoroborate (0.139 g, 0.48 mmol). The mixture was stirred at room temperature for about 20 min then heated at about 80° C. for about 18 h. The solvent was removed in vacuo and the residue was partitioned between water (40 mL) and EtOAc (50 mL). The organic phase was washed with brine (40 mL), dried over magnesium sulfate, filtered and concentrated in vacuo. The residue was purified by silica gel chromatography eluting with 12% EtOAc:heptane to yield the desired product as a yellow solid (0.87 g, 2.7 mmol). Rf (25% EtOAc:heptane) 0.68.

후처리

  1. additionwas added
  2. temperaturethen heated at about 80° C. for about 18 h
  3. customThe solvent was removed in vacuo
  4. customthe residue was partitioned between water (40 mL) and EtOAc (50 mL)
  5. washThe organic phase was washed with brine (40 mL)
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customThe residue was purified by silica gel chromatography
  10. washeluting with 12% EtOAc

출처 및 근거

ORD 기록
ord-3078184b0df7487f8483883e0219f4f9
출처 데이터셋
uspto-grants-2014_06
특허 번호
US08754107B2

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