Cesium carbonate → (R)-methyl 5-(sec-butylamino)-4-cyano-2-methylbenzoate

HRID 906154

반응식

HRID 906154 반응식
[C:1]([C:3]1[C:12](I)=[CH:11][C:6]([C:7]([O:9][CH3:10])=[O:8])=[C:5]([CH3:14])[CH:4]=1)#[N:2].C1(P(C2C=CC3OC4C(=CC=CC=4)CC=3C=2P(C2C=CC=CC=2)C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:61][C@@H:62]([NH2:65])[CH2:63][CH3:64]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[C@H:62]([NH:65][C:12]1[C:3]([C:1]#[N:2])=[CH:4][C:5]([CH3:14])=[C:6]([CH:11]=1)[C:7]([O:9][CH3:10])=[O:8])([CH2:63][CH3:64])[CH3:61]

참가 물질

7

반응물 4

HCID 10796Cesium carbonateHCID 2724537(R)-sec-butylamineHCID 67402433Methyl 4-cyano-5-iodo-2-methylbenzoateHCID 86631950Bis(diphenylphosphino)xanthene

생성물 1

HCID 67404849(R)-methyl 5-(sec-butylamino)-4-cyano-2-methylbenzoate수율 73.4%

시약·촉매·용매 2

HCID 9811564Bis(dibenzylideneacetone)palladium촉매HCID 312751,4-Dioxane용매

반응 조건

온도
95 °C

실험 절차

To a solution of methyl 4-cyano-5-iodo-2-methylbenzoate (500 mg, 1.66 mmol) in 1,4-dioxane (25 mL) was added 9,9-dimethyl-4,5-(bis(diphenylphosphino)xanthene (96 mg, 0.166 mmol), tris(dibenzylideneacetone)-dipalladium (76 mg, 0.083 mmol), cesium carbonate (1.08 g, 3.32 mmol) and (R)-butan-2-amine (506 μL, 4.98 mmol). The reaction mixture was heated to 95° C. and stirred for 16 h, at which time it was cooled to room temperature. The heterogeneous mixture was filtered through a bed of celite, and the filter cake rinsed with ethyl acetate. The filtrate was concentrated, and the residue was purified by flash chromatography (100% hexanes to 5% ethyl acetate in hexanes) to afford (R)-methyl 5-(sec-butylamino)-4-cyano-2-methylbenzoate (300 mg, 73%) as a bright yellow oil. MS (EI) for C14H18N2O2: 247 (MH+).

후처리

  1. temperaturewas cooled to room temperature
  2. filtrationThe heterogeneous mixture was filtered through a bed of celite
  3. washthe filter cake rinsed with ethyl acetate
  4. concentrationThe filtrate was concentrated
  5. customthe residue was purified by flash chromatography (100% hexanes to 5% ethyl acetate in hexanes)

출처 및 근거

ORD 기록
ord-56f4bd5e5abc4c9cb6205e213034de88
출처 데이터셋
uspto-grants-2011_09
특허 번호
US08012956B2

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