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

HRID 16845

반응식

HRID 16845 반응식
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

참가 물질

7

반응물 4

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

생성물 1

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

시약·촉매·용매 2

HCID 167845palladium(II) acetate촉매HCID 312751,4-Dioxane용매

반응 조건

온도
80 °C

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-0491bb1be2c3466bae7581723a930f93
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07737149B2

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