Phenylacetylene → (2-nitro-5-phenylethynylphenyl)-(1-(R)-methyl-2,2-dimethylpropyl)amine

HRID 250749

반응식

HRID 250749 반응식
Cl[C:2]1[CH:3]=[CH:4][C:5]([N+:15]([O-:17])=[O:16])=[C:6]([NH:8][C@H:9]([CH3:14])[C:10]([CH3:13])([CH3:12])[CH3:11])[CH:7]=1.[C:18]1([C:24]#[CH:25])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>CN(C=O)C.C(NCC)C.[Cu]I.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O(C1C=CC=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1)C1C=CC=CC=1P(C1C=CC=CC=1)C1C=CC=CC=1>[N+:15]([C:5]1[CH:4]=[CH:3][C:2]([C:25]#[C:24][C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:7][C:6]=1[NH:8][C@H:9]([CH3:14])[C:10]([CH3:13])([CH3:12])[CH3:11])([O-:17])=[O:16]

참가 물질

8

반응물 2

HCID 10821PhenylacetyleneHCID 66869060(5-Chloro-2-nitrophenyl)-(1-(R)-methyl-2,2-dimethylpropyl)amine

생성물 1

HCID 66868959(2-nitro-5-phenylethynylphenyl)-(1-(R)-methyl-2,2-dimethylpropyl)amine수율 129.2%

시약·촉매·용매 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 167845palladium(II) acetate촉매HCID 4285986Bis[2-(diphenylphosphino)phenyl] ether촉매HCID 6228Dimethylformamide용매HCID 8021Diethylamine용매

실험 절차

Stir (5-Chloro-2-nitrophenyl)-(1-(R)-methyl-2,2-dimethylpropyl)amine (17.23 g, 0.067 mol), copper (I) iodide (0.64 g, 0.0034 mol), (oxydi-2,1-phenylene)bis(diphenylphosphine) (3.61 g, 0.0067 mol), phenylacetylene (12.5 mL, 0.114 mol) in DMF (200 mL) and diethylamine (50 mL) for 5 minutes. Add palladium (II) acetate (0.753 g, 0.0034 mol) and heat to 95° C. for 4 h. Cool to ambient temperature and evaporate off diethylamine under reduced pressure and pour into hexane. Filter insolubles and evaporate off hexane. Dilute with ethyl ether (1 L), filter and wash filtrate with water (2×1 L), saturated sodium chloride, dry magnesium sulfate, concentrate and purify (silica gel chromatography eluting with hexane/dichloromethane mixtures) to give 27.9 g of crude (2-nitro-5-phenylethynylphenyl)-(1-(R)-methyl-2,2-dimethylpropyl)amine that was used in the next step without further purification. To a solution of impure (2-nitro-5-phenylethynylphenyl)-(1-(R)-methyl-2,2-dimethylpropyl)amine (27.9 g) in THF (350 mL), water (100 mL), concentrated ammonium hydroxide (150 mL), Na2S2O4 (73.6 g, 0.423 mol) and stir for about 18 hours. Dilute with ethyl acetate and wash with saturated sodium chloride, dry with magnesium sulfate, concentrate and purify (silica gel chromatography with hexane/dichloromethane mixtures to give 14.51 g of the desired compound (75% for 2 Steps).

후처리

  1. customevaporate off diethylamine under reduced pressure
  2. additionpour into hexane
  3. customFilter insolubles and evaporate off hexane
  4. additionDilute with ethyl ether (1 L)
  5. filtrationfilter
  6. washwash filtrate with water (2×1 L), saturated sodium chloride, dry magnesium sulfate
  7. concentrationconcentrate
  8. custompurify
  9. wash(silica gel chromatography eluting with hexane/dichloromethane mixtures)

출처 및 근거

ORD 기록
ord-fbf4ff9c6e9b42afafe9e00d11a0bb79
출처 데이터셋
uspto-grants-2011_01
특허 번호
US07863310B2

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