Tributylborane → HCID 67012329、化合物

HRID 2354819ノート

反応式

HRID 2354819 の反応式
[CH3:1][CH:2]([CH3:32])[CH2:3][CH2:4][NH:5][C:6]([C:8]1[N:9]=[N:10][C:11]([N:14]2[CH2:19][CH2:18][N:17]([C:20](=[O:31])[C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=3[S:27](C)(=[O:29])=[O:28])[CH2:16][CH2:15]2)=[CH:12][CH:13]=1)=[O:7].C[Mg]Cl.C(B(CCCC)CCCC)CCC.C([O-])(=O)C.[Na+].[NH2:54]OS(O)(=O)=O>C1COCC1.C(OCC)(=O)C.O>[CH3:1][CH:2]([CH3:32])[CH2:3][CH2:4][NH:5][C:6]([C:8]1[N:9]=[N:10][C:11]([N:14]2[CH2:19][CH2:18][N:17]([C:20](=[O:31])[C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][C:22]=3[S:27](=[O:29])(=[O:28])[NH2:54])[CH2:16][CH2:15]2)=[CH:12][CH:13]=1)=[O:7]

参加物

9

反応物 5

HCID 31216TributylboraneHCID 76284hydroxylamine-O-sulfonic acidHCID 517045Sodium AcetateHCID 668499076-[4-(2-METHANESULFONYLBENZOYL)PIPERAZIN-1-YL]PYRIDAZINE-3-CARBOXYLIC Acid (3-METHYLBUTYL)AMIDEHCID 178418332HCID 178418332、化合物

生成物 1

HCID 67012329HCID 67012329、化合物収率 42.1%

試薬・触媒・溶媒 3

HCID 962Water溶媒HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
0 °C

実験手順

To an ice-cold solution of 6-[4-(2-methanesulfonylbenzoyl)piperazin-1-yl]pyridazine-3-carboxylic acid (3-methylbutyl)amide (0.078 g, 0.17 mmol) in 5 mL of THF cooled was added methyl magnesium chloride (0.071 mL, 0.212 mmol). The resulting mixture was stirred for 15 minutes at 0° C., and then 30 minutes at ambient temperature. The reaction mixture was cooled to 0° C. again, then tributylborane (0.255 mL, 0.255 mmol) was added. The mixture was stirred at ambient temperature for 30 minutes, then heated to reflux for 18 h. After the mixture was cooled to 0° C., sodium acetate, water and hydroxylamine-o-sulfonic acid (0.067 g) were added. The mixture was stirred for 3 h, and then diluted with ethyl acetate, washed with saturated sodium bicarbonate, brine, dried and concentrated in vacuo. The residue was purified by flash column chromatography using 20% methanol in ethyl acetate to yield the title product (0.033 g, 42% yield). 1H NMR (300 MHz, CDCl3) δ 8.58, 7.98, 7.81, 7.75-7.68, 7.64-7.58, 7.43, 7.19, 4.03-3.88, 3.78-3.59, 3.21-3.20, 3.152-3.147, 1.65-1.50, 1.46-1.35, 0.85. 13C NMR (75 MHz, CDCl3) δ 170.1, 165.5, 161.7, 146.3, 139.1, 137.3, 135.5, 131.3, 130.9, 128.8, 127.9, 114.4, 45.6, 45.2, 44.96, 42.6, 39.5, 38.8, 27.1, 22.9. MS (ES+) m/z 460.1 (M+1).

後処理

  1. custom30 minutes
  2. customat ambient temperature
  3. temperatureThe reaction mixture was cooled to 0° C. again
  4. stirringThe mixture was stirred at ambient temperature for 30 minutes
  5. temperatureheated
  6. temperatureto reflux for 18 h
  7. temperatureAfter the mixture was cooled to 0° C.
  8. stirringThe mixture was stirred for 3 h
  9. washwashed with saturated sodium bicarbonate, brine
  10. customdried
  11. concentrationconcentrated in vacuo
  12. customThe residue was purified by flash column chromatography

出典と根拠

ORDレコード
ord-7c8c9b5a8cc44cedb100642f609bc64d
出典データセット
uspto-grants-2010_07
特許番号
US07754711B2

反応ノート

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