Cesium carbonate → Ethyl 5-(4-methyl-1,4-diazepan-1-yl)thiophene-2-carboxylate

HRID 16845ノート

反応式

HRID 16845 の反応式
Br[C:2]1[S:6][C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:4][CH:3]=1.[CH3:12][N:13]1[CH2:19][CH2:18][CH2:17][NH:16][CH2:15][CH2:14]1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH3:12][N:13]1[CH2:19][CH2:18][CH2:17][N:16]([C:2]2[S:6][C:5]([C:7]([O:9][CH2:10][CH3:11])=[O:8])=[CH:4][CH:3]=2)[CH2:15][CH2:14]1

参加物

7

反応物 4

HCID 10796Cesium carbonateHCID 2283491-MethylhomopiperazineHCID 605723Ethyl 5-bromothiophene-2-carboxylateHCID 634876Binap, (A+-)-

生成物 1

HCID 66589793Ethyl 5-(4-methyl-1,4-diazepan-1-yl)thiophene-2-carboxylate収率 12.7%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 312751,4-Dioxane溶媒

反応条件

温度
80 °C

実験手順

Palladium(II)acetate (0.135 g, 0.60 mmol) was added to ethyl 5-bromothiophene-2-carboxylate (1.411 g, 6 mmol), 1-methyl-1,4-diazepane (0.822 g, 7.20 mmol), BINAP (0.374 g, 0.60 mmol) and cesium carbonate (2.74 g, 8.40 mmol) in dioxane (40 mL) warmed to 80° C. for 18 h under nitrogen. The crude reaction mixture was purified by ion exchange chromatography, using a SCX column. The desired product was eluted from the column using 7M NH3/MeOH. Fractions were evaporated to dryness to afford the crude product. The crude product was purified by silica column chromatography, eluting with a gradient of 0 to 5% 3M ammonia/MeOH in DCM. Pure fractions were evaporated to dryness to afford ethyl 5-(4-methyl-1,4-diazepan-1-yl)thiophene-2-carboxylate (0.204 g, 12.67%) as a yellow gum.

後処理

  1. customThe crude reaction mixture
  2. customwas purified by ion exchange chromatography
  3. washThe desired product was eluted from the column
  4. customFractions were evaporated to dryness
  5. customto afford the crude product
  6. customThe crude product was purified by silica column chromatography
  7. washeluting with a gradient of 0 to 5% 3M ammonia/MeOH in DCM
  8. customPure fractions were evaporated to dryness

出典と根拠

ORDレコード
ord-0491bb1be2c3466bae7581723a930f93
出典データセット
uspto-grants-2010_06
特許番号
US07737149B2

反応ノート

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