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2-Chlorobenzaldehyde → 2-[(2-chloro-phenyl)-hydroxy-methyl]-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one

HRID 1455259
ノート
印刷プレビュー

反応式

HRID 1455259 の反応式
I[C:2]1[C:9](=[O:10])[N:5]2[CH2:6][CH2:7][CH2:8][N:4]2[C:3]=1[C:11]1[CH:16]=[CH:15][N:14]=[C:13]([S:17][CH3:18])[N:12]=1.C([Mg]Cl)(C)C.[Cl:24][C:25]1[CH:32]=[CH:31][CH:30]=[CH:29][C:26]=1[CH:27]=[O:28]>C1COCC1>[Cl:24][C:25]1[CH:32]=[CH:31][CH:30]=[CH:29][C:26]=1[CH:27]([OH:28])[C:2]1[C:9](=[O:10])[N:5]2[CH2:6][CH2:7][CH2:8][N:4]2[C:3]=1[C:11]1[CH:16]=[CH:15][N:14]=[C:13]([S:17][CH3:18])[N:12]=1
参加物反応条件実験手順後処理出典と根拠反応ノート

参加物

5

反応物 3

HCID 69962-ChlorobenzaldehydeHCID 575317902-iodo-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-oneHCID 178418918HCID 178418918、化合物

生成物 1

HCID 575317942-[(2-chloro-phenyl)-hydroxy-methyl]-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one収率 58%

試薬・触媒・溶媒 1

HCID 8028
Tetrahydrofuran
溶媒
2 回

反応条件

温度
-40 °C

実験手順

To a cold (−40° C.) suspension of 2-iodo-3-(2-methylsulfanyl-pyrimidin-4-yl)-6,7-dihydro-5H-pyrazolo[1,2-a]pyrazol-1-one, 21, (0.40 g, 1.07 mmol) in THF (3 mL) is added dropwise isopropyl-magnesium chloride (0.59 mL of a 2M solution in THF, 1.18 mmol). After stirring for 30 min at −40° C., a solution of 2-chlorobenzaldehyde (0.16 mL, 1.40 mmol) is added dropwise. The reaction mixture is allowed to warm to 0° C. over 1 h period. The mixture is quenched by pouring into aqueous saturated NH4Cl. The aqueous phase is extracted three times with EtOAc and the combined organic phases are dried (MgSO4), filtered and concentrated in vacuo. The crude residue is purified over silica (10% MeOH/chloroform) to afford 240 mg (58% yield) of desired product. 1H NMR (300 MHz, CDCl3) δ 8.56 (d, J=5.1 Hz, 1H), 7.78 (dd, J=7.2, 1.8 Hz, 1H), 7.34-7.18 (m, 2H), 7.01 (d, J=5.1 Hz, 1H), 6.21 (s, 1H), 4.20-4.01 (m, 5H), 2.80-2.70 (m, 2H), 2.58 (s, 3H); ESI+ MS: m/z (rel intensity) 371.1 (100, M++H).

後処理

  1. temperatureto warm to 0° C. over 1 h period
  2. customThe mixture is quenched
  3. additionby pouring into aqueous saturated NH4Cl
  4. extractionThe aqueous phase is extracted three times with EtOAc
  5. dry with materialthe combined organic phases are dried (MgSO4)
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customThe crude residue is purified over silica (10% MeOH/chloroform)

出典と根拠

ORDレコード
ord-ead8f192c9114bf9a4d87d9af0f47149
出典データセット
uspto-grants-2009_01
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US07482356B2

反応ノート

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