N,N'-Dimethylethylenediamine → methyl 4-{1-hydroxy-1-[1-(3-methyl-5-{[4-(trifluoromethyl)pyrimidin-2-yl]amino}phenyl)-1H-pyrazol-4-yl]ethyl}benzoate

HRID 595300

反応式

HRID 595300 の反応式
[OH:1][C:2]([C:9]1[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][CH:10]=1)([C:4]1[CH:5]=[N:6][NH:7][CH:8]=1)[CH3:3].Br[C:20]1[CH:21]=[C:22]([NH:27][C:28]2[N:33]=[C:32]([C:34]([F:37])([F:36])[F:35])[CH:31]=[CH:30][N:29]=2)[CH:23]=[C:24]([CH3:26])[CH:25]=1.CNCCNC.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C(OCC)(=O)C.[Cu]I>[OH:1][C:2]([C:9]1[CH:18]=[CH:17][C:12]([C:13]([O:15][CH3:16])=[O:14])=[CH:11][CH:10]=1)([C:4]1[CH:5]=[N:6][N:7]([C:20]2[CH:21]=[C:22]([NH:27][C:28]3[N:33]=[C:32]([C:34]([F:37])([F:36])[F:35])[CH:31]=[CH:30][N:29]=3)[CH:23]=[C:24]([CH3:26])[CH:25]=2)[CH:8]=1)[CH3:3]

参加物

8

反応物 4

HCID 8070N,N'-DimethylethylenediamineHCID 10796Cesium carbonateHCID 58456396N-(3-bromo-5-methylphenyl)-4-(trifluoromethyl)pyrimidin-2-amineHCID 118208644methyl 4-[1-hydroxy-1-(1H-pyrazol-4-yl)ethyl]benzoate

生成物 1

HCID 118208752methyl 4-{1-hydroxy-1-[1-(3-methyl-5-{[4-(trifluoromethyl)pyrimidin-2-yl]amino}phenyl)-1H-pyrazol-4-yl]ethyl}benzoate

試薬・触媒・溶媒 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8857Ethyl Acetate溶媒HCID 312751,4-Dioxane溶媒

反応条件

温度
130 °C

実験手順

A mixture of methyl 4-[1-hydroxy-1-(1H-pyrazol-4-yl)ethyl]benzoate (17 mg, 0.053 mmol), N-(3-bromo-5-methylphenyl)-4-(trifluoromethyl)pyrimidin-2-amine (13 mg, 0.053 mmol), copper(I) iodide (1 mg, 0.005 mmol), N1,N2-dimethylethane-1,2-diamine (0.47 mg, 0.005 mmol), and cesium carbonate (52 mg, 0.16 mmol) in 1,4-dioxane (2 mL) was stirred at 130° C. for 50 minutes. After being cooled to room temperature, the mixture was diluted with ethyl acetate and washed with brine. The organic layer was concentrated and the residue was purified by preparative thin layer chromatography to afford methyl 4-{1-hydroxy-1-[1-(3-methyl-5-{[4-(trifluoromethyl)pyrimidin-2-yl]amino}phenyl)-1H-pyrazol-4-yl]ethyl}benzoate. MS ESI calc'd. for C25H23F3N5O3 [M+H]+ 498. found 498. 1H NMR (400 MHz, CDCl3): δ 8.66 (s, 1H), 8.02-8.06 (m, 3H), 7.78 (s, 1H), 7.59-7.63 (m, 3H), 7.51 (s, 1H), 7.18 (s, 1H), 7.06 (s, 1H), 3.92 (s, 3H), 3.79 (s, 1H), 3.49 (s, 1H), 2.41 (s, 3H), 1.97 (s, 3H).

後処理

  1. temperatureAfter being cooled to room temperature
  2. washwashed with brine
  3. concentrationThe organic layer was concentrated
  4. customthe residue was purified by preparative thin layer chromatography

出典と根拠

ORDレコード
ord-597e17d7e95e49f48fbef0c8a75fcbae
出典データセット
uspto-grants-2016_01
特許番号
US09242984B2

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