Dimethyl Sulfoxide → ethyl 2-(1-oxo-6-vinylphthalazin-2(1H)-yl)acetate

HRID 587232ノート

反応式

HRID 587232 の反応式
[CH:1]([C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[C:9](=[O:13])[NH:8][N:7]=[CH:6]2)=[CH2:2].BrC1C=C2[C:22](=CC=1)[C:21](=[O:25])NN=C2.[C:26]([O-:29])([O-])=O.[K+].[K+].[CH3:32]S(C)=O>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[O:13]=[C:9]1[C:10]2[C:5](=[CH:4][C:3]([CH:1]=[CH2:2])=[CH:12][CH:11]=2)[CH:6]=[N:7][N:8]1[CH2:32][C:26]([O:25][CH2:21][CH3:22])=[O:29]

参加物

6

反応物 4

HCID 679Dimethyl SulfoxideHCID 11430Potassium CarbonateHCID 115359186-Bromophthalazin-1(2h)-oneHCID 866751746-vinylphthalazine-1(2H)-one

生成物 1

HCID 86675173ethyl 2-(1-oxo-6-vinylphthalazin-2(1H)-yl)acetate収率 63%

試薬・触媒・溶媒 1

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒

反応条件

温度
80 °C

実験手順

6-Vinylphthalazine-1(2H)-one (BI27): A solution of 6-bromophthalazine-1 (2H)-one (0.25 g, 1.11 mmol), potassium vinyl trifluoroborate (0.446 g, 3.33 mmol) and K2CO3 (0.46 g, 3.33 mmol) in DMSO (2 mL) was degassed with argon for 20 min at ambient temperature. PdCl2(dppf) (0.04 g, 0.055 mmol) was added at ambient temperature, and the reaction mixture was heated to 80° C. for 2 h. The reaction mixture was cooled to ambient temperature and filtered through Celite® bed under vacuum and washed with EtOAc. The reaction mixture was extracted with EtOAc and the combined EtOAc layer dried over Na2SO4 and concentrated under reduced pressure to afford the crude product. The crude compound was purified by column chromatography (SiO2, 100-200 mesh; 50% EtOAc/petroleum ether) to afford the title compound as a brown solid (0.12 g, 63%): 1H NMR (400 MHz, DMSO-d6) δ 13.61 (br, 1H), 8.33 (m, 1H), 8.19 (m, 1H), 8.01 (m, 2H), 6.97 (m, 1H), 6.15 (m, 1H), 5.56 (d, J=10.8 Hz, 1H); ESIMS m/z 172.93 ([M+H]+); IR (thin film) 1748, 1655, 3241 cm−1.

後処理

  1. temperatureThe reaction mixture was cooled to ambient temperature
  2. filtrationfiltered through Celite® bed under vacuum
  3. washwashed with EtOAc
  4. extractionThe reaction mixture was extracted with EtOAc
  5. dry with materialthe combined EtOAc layer dried over Na2SO4
  6. concentrationconcentrated under reduced pressure
  7. customto afford the crude product
  8. customThe crude compound was purified by column chromatography (SiO2, 100-200 mesh; 50% EtOAc/petroleum ether)

出典と根拠

ORDレコード
ord-08cf8d08ff514330a584173bb96ecfa0
出典データセット
uspto-grants-2016_01
特許番号
US09226500B2

反応ノート

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