3-(Trimethylstannyl)pyridine → 3-[5-bromo-3-(2-trimethylsilanyl-ethoxymethyl)-3H-imidazol-4-yl]-pyridine

HRID 660189

反応式

HRID 660189 の反応式
C[Sn](C)(C)[C:3]1[CH:4]=[N:5][CH:6]=[CH:7][CH:8]=1.[Br:11][C:12]1[N:13]=[CH:14][N:15]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:16]=1Br>C1(C)C=CC=CC=1.C(OCC)(=O)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[Br:11][C:12]1[N:13]=[CH:14][N:15]([CH2:18][O:19][CH2:20][CH2:21][Si:22]([CH3:25])([CH3:24])[CH3:23])[C:16]=1[C:3]1[CH:4]=[N:5][CH:6]=[CH:7][CH:8]=1

参加物

6

反応物 2

HCID 108684453-(Trimethylstannyl)pyridineHCID 154245214,5-dibromo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-imidazole2 回

生成物 1

HCID 575480803-[5-bromo-3-(2-trimethylsilanyl-ethoxymethyl)-3H-imidazol-4-yl]-pyridine収率 36%

試薬・触媒・溶媒 3

HCID 6102075Dichlorobis(triphenylphosphine)palladium触媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of 71 (0.82 g, 3.4 mmol) in anhydrous toluene (50 ml) were added 0.9 eq (1.10 g) of 4,5-dibromo-1-(2-trimethylsilanyl-ethoxymethyl)-1H-imidazole (compound 72, LCMS (method A): Rt: 3.60 min, ([M+H]+=357)) and the resulting mixture was stirred for 2 hours under N2 (room temperature). To this reaction mixture were added 10 mol % of PdCl2(PPH3)2 (240 mg). After the addition, the temperature was raised to 100° C. and the resulting solution was stirred for 18 hours under N2. The reaction mixture was cooled, diluted with ethyl acetate, washed three times with a saturated NaHCO3 solution, dried (Na2SO4), filtered and concentrated. The resulting residue was purified by flash chromatography (diethyl ether followed by ethyl acetate) to afford 3-[5-bromo-3-(2-trimethylsilanyl-ethoxymethyl)-3H-imidazol-4-yl]-pyridine (73) as an oil (385 mg, 36%). LCMS (method A): Rt: 3.40 min, ([M+H]+=355). 1H-NMR (400 MHz, CDCl3 and HMBC): δ 8.79 (d, J=2 Hz, 1H), 8.66 (dd, J=5 Hz, 2 Hz, 1H), 7.91 (dt, J=8 Hz, 2 Hz, 1H), 7.66 (s, 1H), 7.44-7.40 (m, 1H), 5.17 (s, 2H), 3.56-3.50 (m, 2H), 0.94-0.87 (m, 2H), 0.0 (s, 9H).

後処理

  1. additionAfter the addition
  2. temperaturethe temperature was raised to 100° C.
  3. stirringthe resulting solution was stirred for 18 hours under N2
  4. temperatureThe reaction mixture was cooled
  5. washwashed three times with a saturated NaHCO3 solution
  6. dry with materialdried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe resulting residue was purified by flash chromatography (diethyl ether followed by ethyl acetate)

出典と根拠

ORDレコード
ord-cbcc89bcb1fb46c685d20f44bf02545d
出典データセット
uspto-grants-2011_12
特許番号
US08084473B2

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