Cesium carbonate → Ethyl 4-cyano-3-(pentan-3-ylamino)benzoate

HRID 906174ノート

反応式

HRID 906174 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[C:13]#[N:14])[C:5]([O:7][CH2:8][CH3:9])=[O:6].C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:21][CH2:22][CH:23]([NH2:26])[CH2:24][CH3:25].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>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].O1CCOCC1>[C:13]([C:12]1[CH:11]=[CH:10][C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])=[CH:3][C:2]=1[NH:26][CH:23]([CH2:24][CH3:25])[CH2:22][CH3:21])#[N:14]

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 120193-PentanamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 18374323Ethyl 3-bromo-4-cyanobenzoate

生成物 1

HCID 67402973Ethyl 4-cyano-3-(pentan-3-ylamino)benzoate収率 61.4%

試薬・触媒・溶媒 2

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
95 °C

実験手順

To a pressure vessel were added ethyl 3-bromo-4-cyanobenzoate (500 mg, 1.97 mmol), cesium carbonate (1.28 g, 3.94 mmol), pentan-3-amine (688 uL, 5.90 mmol), XANTPHOS (114 mg, 0.20 mmol), tris(dibenzylideneacetone)dipalladium(0) (90 mg, 0.10 mmol), and dioxane (3 mL). The vessel was sealed and heated to 95° C. for 15 h. After cooling to room temperature, the mixture was filtered through celite and the filter cake rinsed with ethyl acetate. The filtrate was then concentrated and the residue was purified by column chromatography (10% ethyl acetate in hexanes) to provide ethyl 4-cyano-3-(pentan-3-ylamino)benzoate (315 mg, 1.21 mmol, 61% yield) as a yellow syrup. 1H NMR (400 MHz, CDCl3): 7.43 (d, 1H), 7.33 (s, 1H), 7.25 (dd, 1H), 4.44-4.35 (m, 3H), 3.48-3.40 (m, 1H), 1.72-1.48 (m, 4H), 1.40 (t, 3H), 0.96 (t, 6H); MS (EI) for C15H20N2O2: 261 (MH+).

後処理

  1. customThe vessel was sealed
  2. temperatureAfter cooling to room temperature
  3. filtrationthe mixture was filtered through celite
  4. washthe filter cake rinsed with ethyl acetate
  5. concentrationThe filtrate was then concentrated
  6. customthe residue was purified by column chromatography (10% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-33a35fad81244927ab87bc72fcdaf14d
出典データセット
uspto-grants-2011_09
特許番号
US08012956B2

反応ノート

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