Cesium carbonate → 1-[2,5-Bis(methyloxy)-4-nitrophenyl]-4-(1-methylethyl)piperazine

HRID 1014212ノート

反応式

HRID 1014212 の反応式
Cl[C:2]1[CH:7]=[C:6]([O:8][CH3:9])[C:5]([N+:10]([O-:12])=[O:11])=[CH:4][C:3]=1[O:13][CH3:14].[CH:15]([N:18]1[CH2:23][CH2:22][NH:21][CH2:20][CH2:19]1)([CH3:17])[CH3:16].C(=O)([O-])[O-].[Cs+].[Cs+].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>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]>[CH3:14][O:13][C:3]1[CH:4]=[C:5]([N+:10]([O-:12])=[O:11])[C:6]([O:8][CH3:9])=[CH:7][C:2]=1[N:21]1[CH2:22][CH2:23][N:18]([CH:15]([CH3:17])[CH3:16])[CH2:19][CH2:20]1

参加物

6

反応物 4

HCID 10796Cesium carbonateHCID 780131-IsopropylpiperazineHCID 813621-Chloro-2,5-dimethoxy-4-nitrobenzeneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)

生成物 1

HCID 594421271-[2,5-Bis(methyloxy)-4-nitrophenyl]-4-(1-methylethyl)piperazine収率 76%

試薬・触媒・溶媒 1

HCID 9811564Bis(dibenzylideneacetone)palladium触媒

反応条件

温度
100 °C

実験手順

1-chloro-2,5-bis(methyloxy)-4-nitrobenzene (3.25 g, 15 mmol, TCl America), isopropylpiperizine (3.84 g, 30 mmol, Oakwood Products), cesium carbonate (9.8 g, 30 mmol), Pd2dba3 (1.37 g, 1.5 mmol), and XANTPHOS (1.3 g, 2.25 mmol) were added to degassed dioxane (80 mL) and heated to 100° C. under a water cooled reflux condenser for 12 hours. The dioxane was removed under reduced pressure and the solids were partitioned between methylene chloride (500 mL) and water (500 mL). The organic layer was dried over sodium sulfate, taken to a residue under reduced pressure, and purified by chromatography on SiO2to give 1-[2,5-bis(methyloxy)-4-nitrophenyl]-4-(1-methylethyl)piperazine as a yellow solid (3.5 g, 11.3 mmol, 76% yield). 1H NMR (400 MHz, CDCl3) δ ppm 1.09 (d, J=6.60 Hz, 6 H), 2.69-2.73 (m, 4 H), 2.75 (d, J=6.60 Hz, 1 H), 3.23-3.32 (m, 4 H), 3.88 (s, 3 H), 3.94 (s, 3 H), 6.48 (s, 1 H), 7.55 (s, 1 H).

後処理

  1. customto degassed dioxane (80 mL)
  2. temperaturecooled
  3. temperaturereflux condenser for 12 hours
  4. customThe dioxane was removed under reduced pressure
  5. customthe solids were partitioned between methylene chloride (500 mL) and water (500 mL)
  6. dry with materialThe organic layer was dried over sodium sulfate
  7. custompurified by chromatography on SiO2to

出典と根拠

ORDレコード
ord-9bb07c05cb8548be8278c6d19ba8869d
出典データセット
uspto-grants-2011_07
特許番号
US07981903B2

反応ノート

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