Azidomethyl 2,2-dimethylpropanoate → (4-(4-(4-amino-3-fluorophenoxy)pyridin-2-yl)-1H-1,2,3-triazol-1-yl)methyl pivalate

HRID 450476ノート

反応式

HRID 450476 の反応式
[C:1]([O:7][CH2:8][N:9]=[N+:10]=[N-:11])(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3].[C:12]([C:14]1[CH:19]=[C:18]([O:20][C:21]2[CH:26]=[CH:25][C:24]([NH2:27])=[C:23]([F:28])[CH:22]=2)[CH:17]=[CH:16][N:15]=1)#[CH:13].O=C1O[C@H]([C@H](CO)O)C([O-])=C1O.[Na+]>C(O)(C)(C)C.O.CCOC(C)=O.S([O-])([O-])(=O)=O.[Cu+2]>[C:1]([O:7][CH2:8][N:9]1[CH:13]=[C:12]([C:14]2[CH:19]=[C:18]([O:20][C:21]3[CH:26]=[CH:25][C:24]([NH2:27])=[C:23]([F:28])[CH:22]=3)[CH:17]=[CH:16][N:15]=2)[N:11]=[N:10]1)(=[O:6])[C:2]([CH3:5])([CH3:4])[CH3:3]

参加物

8

反応物 3

HCID 11521126Azidomethyl 2,2-dimethylpropanoateHCID 23667548Sodium AscorbateHCID 598255834-(2-Ethynylpyridin-4-yloxy)-2-fluorobenzenamine

生成物 1

HCID 67399290(4-(4-(4-amino-3-fluorophenoxy)pyridin-2-yl)-1H-1,2,3-triazol-1-yl)methyl pivalate収率 90%

試薬・触媒・溶媒 4

HCID 24462Copper Sulfate触媒HCID 962Water溶媒3 回HCID 6386tert-Butanol溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a suspension of azidomethyl pivalate (0.075 g, 0.477 mmol), 4-(2-ethynylpyridin-4-yloxy)-2-fluorobenzenamine from Example A21 (0.109 g, 0.477 mmol) in t-butanol (0.6 mL) and water (0.6 mL) was added sodium ascorbate (0.021 g, 0.095 mmol). Copper(II)sulfate in water (0.048 ml, 0.048 mmol) was added to the above suspension and the dark red mixture was stirred for 3 h at RT. It was diluted with water (30 mL) and EtOAc (20 mL), the layers were separated and the aqueous layer was extracted with EtOAc (2×15 mL). The combined organics were washed with brine, dried (Na2SO4) and concentrated to afford (4-(4-(4-amino-3-fluorophenoxy)pyridin-2-yl)-1H-1,2,3-triazol-1-yl)methyl pivalate as a red solid. (0.165 g, 90% yield). 1H NMR (400 MHz, DMSO-d6): δ 8.54 (s, 1H), 8.46 (brs, 1H), 7.60 (s, 1H), 6.98 (d, J=8.8 Hz, 1H), 6.94 (d, J=3.6 Hz, 1H), 6.83-6.81 (m, 2H), 6.42 (s, 2H), 4.78 (s, 2H), 1.17 (s, 9H); MS (ESI) m/z: 386.1 (M+H+).

後処理

  1. customthe layers were separated
  2. extractionthe aqueous layer was extracted with EtOAc (2×15 mL)
  3. washThe combined organics were washed with brine
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated

出典と根拠

ORDレコード
ord-ef1b22eed3784c7fabd77a100bf2b7f1
出典データセット
uspto-grants-2013_07
特許番号
US08486951B2

反応ノート

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