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Nitrogen → 7-(1-Ethyl-propyl)-3-(2,4-dichloro-thiazol-5-yl)-2,5-dimethyl-pyrazolo[1,5-a]pyrimidine

HRID 1044662
ノート
印刷プレビュー

反応式

HRID 1044662 の反応式
[CH2:1]([CH:3]([C:6]1[N:11]2[N:12]=[C:13]([CH3:16])[C:14](I)=[C:10]2[N:9]=[C:8]([CH3:17])[CH:7]=1)[CH2:4][CH3:5])[CH3:2].[O-]P([O-])([O-])=O.[K+].[K+].[K+].[Cl:26][C:27]1[S:28][CH:29]=[C:30]([Cl:32])[N:31]=1.N1C2C(=CC=C3C=2N=CC=C3)C=CC=1.N#N>[Cu]I.CC(N(C)C)=O>[CH2:1]([CH:3]([C:6]1[N:11]2[N:12]=[C:13]([CH3:16])[C:14]([C:29]3[S:28][C:27]([Cl:26])=[N:31][C:30]=3[Cl:32])=[C:10]2[N:9]=[C:8]([CH3:17])[CH:7]=1)[CH2:4][CH3:5])[CH3:2]
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

8

反応物 5

HCID 947NitrogenHCID 13181,10-PhenanthrolineHCID 62657Potassium Phosphate, TribasicHCID 123331552,4-DichlorothiazoleHCID 248985233-Iodo-2,5-dimethyl-7-(pentan-3-yl)pyrazolo[1,5-a]pyrimidine

生成物 1

HCID 452757037-(1-Ethyl-propyl)-3-(2,4-dichloro-thiazol-5-yl)-2,5-dimethyl-pyrazolo[1,5-a]pyrimidine
収率 70%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 31374Dimethylacetamide溶媒

反応条件

温度
120 °C

実験手順

Charge 7-(1-ethyl-propyl)-3-iodo-2,5-dimethyl-pyrazolo[1,5-a]pyrimidine (1.03 g, 3.00 mmoles), K3PO4 (1.95 g, 9.00 mmoles), 2,4-dichlorothiazole (0.58 g, 3.75 mmoles), 1,10 phenanthroline (0.05 g, 0.30 mmoles) and anhydrous DMAC (5 mL) to a round bottom flask equipped with a magnetic stir bar, thermal couple and N2 inlet. Degas the yellow heterogeneous reaction mixture with N2 (gas) for 30 min. and then add CuI (0.06 g, 0.30 mmoles) in one portion followed by additional 30 min. degassing with N2 (gas). Stir the reaction mixture at 120° C. for about 6 hr. Cool the reaction mixture to room temperature overnight, add toluene (10 mL) and stir for 1 hr. Purify the mixture through silica gel eluting with toluene (10 ml). Extract with 1 M HCl (10 mL), water (10 mL), brine (10 mL) and concentrate under reduced pressure to give a yellow solid. Recrystallize the solid from methanol (5 ml) to yield the title compound as a yellow crystalline solid. (0.78 g, 70% yield, >99% pure by LC) MS (ES)=369 (M+1). 1H NMR (CDCl3)=6.5 (1H, s); 3.6 (1H, m); 2.6 (3H, s); 2.5 (3H, s); 1.9 (4H, m); 0.9 (6H, t).

後処理

  1. customequipped with a magnetic stir bar
  2. customDegas the yellow heterogeneous reaction mixture with N2 (gas) for 30 min.
  3. customdegassing with N2 (gas)
  4. temperatureCool the reaction mixture to room temperature overnight
  5. additionadd toluene (10 mL)
  6. stirringstir for 1 hr
  7. customPurify the mixture through silica gel eluting with toluene (10 ml)
  8. extractionExtract with 1 M HCl (10 mL), water (10 mL), brine (10 mL)
  9. concentrationconcentrate under reduced pressure
  10. customto give a yellow solid
  11. customRecrystallize the solid from methanol (5 ml)

出典と根拠

ORDレコード
ord-e81da3655835453dae1e8e6d9352def3
出典データセット
uspto-grants-2013_10
DOI
10.6084/m9.figshare.5104873.v1
特許番号
US08563718B2

反応ノート

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