Potassium Carbonate → 4-(1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazol-3-yl)aniline

HRID 62034

反応式

HRID 62034 の反応式
Br[C:2]1[N:6]=[CH:5][N:4]([C:7]2[CH:12]=[CH:11][C:10]([C:13]([F:16])([F:15])[F:14])=[CH:9][CH:8]=2)[N:3]=1.CC1(C)C(C)(C)OB([C:25]2[CH:31]=[CH:30][C:28]([NH2:29])=[CH:27][CH:26]=2)O1.C(=O)([O-])[O-].[K+].[K+]>COCCOC.O.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[F:14][C:13]([F:16])([F:15])[C:10]1[CH:11]=[CH:12][C:7]([N:4]2[CH:5]=[N:6][C:2]([C:25]3[CH:31]=[CH:30][C:28]([NH2:29])=[CH:27][CH:26]=3)=[N:3]2)=[CH:8][CH:9]=1

参加物

7

反応物 3

HCID 11430Potassium CarbonateHCID 27346204-(Tetramethyl-1,3,2-dioxaborolan-2-yl)anilineHCID 904043003-bromo-1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazole

生成物 1

HCID 893731204-(1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazol-3-yl)aniline収率 74.5%

試薬・触媒・溶媒 3

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 962Water溶媒HCID 80711,2-Dimethoxyethane溶媒

反応条件

温度
120 °C

実験手順

To 3-bromo-1-(4-(trifluoromethyl)phenyl)-1H-1,2,4-triazole (5.64 g, 18.35 mmol) was added 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (7.42 g, 33.9 mmol), tetrakis(triphenylphosphine) palladium(0) (3.30 g, 2.86 mmol), and potassium carbonate (7.82 g, 56.6 mmol) in 1,2-dimethoxyethane (75 mL) and water (18 mL). The mixture was degassed with nitrogen for 10 minutes. The reaction mixture was heated at 120° C. for 20 h. The reaction was cooled to room temperature and diluted with ethyl acetate (100 mL). The resultant salts were filtered and the filtrated layers were separated. The aqueous layer was separated with ethyl acetate (2×25 mL). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated onto Celite®. Purification by silica gel chromatography using 0-100% ethyl acetate/hexanes as eluent provided the title compound as a yellow solid (4.16 g, 68%): 1H NMR (400 MHz, CDCl3) δ 8.60 (s, 1H), 8.03-7.97 (m, 2H), 7.88 (d, J=8.4 Hz, 2H), 7.77 (d, J=8.5 Hz, 2H), 6.79-6.74 (m, 2H), 3.88 (s, 2H); 13C NMR (101 MHz, CDCl3) δ 163.94, 148.07, 139.68, 129.67, 129.34, 128.04, 127.07, 127.04, 127.00, 126.96, 125.05, 120.50, 119.35, 114.87; 19F NMR (376 MHz, CDCl3) δ −62.43; ESIMS m/z 305.1 ([M+H]+).

後処理

  1. customThe mixture was degassed with nitrogen for 10 minutes
  2. temperatureThe reaction was cooled to room temperature
  3. additiondiluted with ethyl acetate (100 mL)
  4. filtrationThe resultant salts were filtered
  5. customthe filtrated layers were separated
  6. customThe aqueous layer was separated with ethyl acetate (2×25 mL)
  7. dry with materialThe combined organic layers were dried over anhydrous magnesium sulfate
  8. concentrationconcentrated onto Celite®
  9. customPurification by silica gel chromatography

出典と根拠

ORDレコード
ord-11d90400b44c41d88f7b2be19367c6e3
出典データセット
uspto-grants-2016_09
特許番号
US09445594B2

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