Cyclohexylamine → Benzyl 4-cyano-3-(cyclohexylamino)benzoate

HRID 906146ノート

反応式

HRID 906146 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:15]=[CH:16][C:17]=1[C:18]#[N:19])[C:5]([O:7][CH2:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1)=[O:6].C(=O)([O-])[O-].[Cs+].[Cs+].[CH:26]1([NH2:32])[CH2:31][CH2:30][CH2:29][CH2:28][CH2:27]1.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>C(OCC)(=O)C.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:18]([C:17]1[CH:16]=[CH:15][C:4]([C:5]([O:7][CH2:8][C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[O:6])=[CH:3][C:2]=1[NH:32][CH:26]1[CH2:31][CH2:30][CH2:29][CH2:28][CH2:27]1)#[N:19]

参加物

8

反応物 4

HCID 7965CyclohexylamineHCID 10796Cesium carbonateHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 67404157Benzyl 3-bromo-4-cyanobenzoate

生成物 1

HCID 67405391Benzyl 4-cyano-3-(cyclohexylamino)benzoate収率 75%

試薬・触媒・溶媒 3

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
95 °C

実験手順

To a pressure vessel were added benzyl 3-bromo-4-cyanobenzoate (150 mg, 0.47 mmol) prepared as described in example 11 (steps 1, 2), cesium carbonate (310 mg, 0.95 mmol), cyclohexylamine (108 uL, 0.95 mmol), XANTPHOS (27 mg, 0.047 mmol), tris(dibenzylideneacetone)dipalladium(0) (21 mg, 0.023 mmol), and dioxane (3 mL). The vessel was sealed and heated to 95° C. for 4 h. After cooling to room temperature, the mixture was diluted with ethyl acetate and was washed with water. The aqueous phase was extracted with ethyl acetate. The combined organic extracts were dried over magnesium sulfate, filtered, and concentrated. The residue was purified by column chromatography (10% ethyl acetate in hexanes) to provide benzyl 4-cyano-3-(cyclohexylamino)benzoate (118 mg, 0.35 mmol, 75% yield) as a yellow syrup. 1H NMR (400 MHz, CDCl3): 7.45-7.30 (m, 7H), 7.27 (dd, 1H), 5.36 (s, 2H), 4.56 (d, 1H), 3.48-3.38 (m, 1H), 2.08-2.01 (m, 2H), 1.83-1.75 (m, 2H), 1.71-1.64 (m, 1H), 1.46-1.35 (m, 2H), 1.31-1.20 (m, 3H); MS (EI) for C21H22N2O2: 333 (M−H).

後処理

  1. customprepared
  2. customThe vessel was sealed
  3. temperatureAfter cooling to room temperature
  4. washwas washed with water
  5. extractionThe aqueous phase was extracted with ethyl acetate
  6. dry with materialThe combined organic extracts were dried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by column chromatography (10% ethyl acetate in hexanes)

出典と根拠

ORDレコード
ord-a741229b11624418815c947ba60379a8
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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